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US4910321A - Living catalysts, complexes and polymers therefrom - Google Patents

Living catalysts, complexes and polymers therefrom Download PDF

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US4910321A
US4910321A US07/156,538 US15653888A US4910321A US 4910321 A US4910321 A US 4910321A US 15653888 A US15653888 A US 15653888A US 4910321 A US4910321 A US 4910321A
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olefin
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Joseph P. Kennedy
Rudolf Faust
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AKRON AN OHIO STATE UNIVERSITY, University of
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

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  • This invention relates to a novel class of complexes, useful as living polymerization catalysts to produce novel polymers having specific end groups and especially new type polymers such as butyl rubber and related polymers. More particularly, this invention relates to novel complex compounds containing or incorporating at least one or a number of olefinic monomers but sufficient to give a range of molecular weights from the very low range of about 200, 500 or 10,000 to the extremely high range of 500,000 or a million and higher. Specifically, this invention provides a so-called living polymer preparation method that allows polymers to be made as homopolymers, random copolymers, to highly specialized block copolymers, or terpolymers, and the like.
  • Living polymerizations are not only of scientific interest, but also of great commercial consequence, and several industrial processes are based on living systems, e.g., cis-1,4-polybutadiene, triblock copolymers of styrene/butadiene/styrene, polytetrahydrofuran, but these are not carbocationic polymerization processes.
  • This invention concerns a new family of initiating systems, a new process for making polymers and a series of new products having specific end groups thereon.
  • R 1 in the above formula may be H, halogen, an organic moiety such as methyl and related alkyl, or aryl groups, preferably up to about 14 to 20 carbon atoms, alkylene groups such as --CH ⁇ CH 2 and related lower alkylene groups, preferably 2 to about 8 carbon atoms, and groups containing hetero atoms and related groups such as alkylene chloride, methylene to butylene alkoxy, preferably up to about 14 to 20 carbon atoms;
  • R 2 may be H, methyl and related alkyl groups containing preferably from 1 to about 14 to 20 carbon atoms, in general R 2 can be the same as R 1 ;
  • R 3 may be methyl, or related alkyls of preferably 2 to about 20 carbon atoms or aryls such as phenyl, cycloalkyls, or vinyl or allyl groups or a CH 2 ⁇ group, in general R 3 can be the same as R 2 ;
  • R 4 may be (CH 2 ) x , or other moiety such as --CH 2 --CH 2 --, acetylenic such as --C.tbd.C--, or arylene such as ##STR2## or ethylenic such as --CH ⁇ CH-- and related homologous groups; where x is 1 to about 20 and preferably 1 to 10 in value;
  • R 5 may be alkylenes such as --CH 2 --, and substituted alkylenes such as ##STR3## or other well known groups where H and methyl have been replaced to produce the related homologous series that yield many lactones having alkyl, aryl, alkaryl, arylalkyl and cycloalkyl groups substituted on the carbon in the lactone ring;
  • R 6 may be the same as R 1 but preferably limited to H or alkyls such as methyl or ethyl or aryl;
  • R 7 is an alkylene group containing carbon atoms to complete the lactone ring over the range of 3 to about 20 carbon atoms or more or an alkylene group having the hydrogen atoms on at least one of the carbon atoms substituted with other carbon atoms or customary carbon atoms substituents;
  • R 8 may be a three valent organic moiety such as ##STR4##
  • R 2 in the above formulae can be the same or different.
  • the polymerization can be carried out at an appropriate temperature by contacting preferably in a liquid diluent the olefinic monomer or monomers, the organic acid or ester and BCl 3 or related Lewis acid.
  • the diluents preferably are hydrocarbons such as n-butane, n-pentane, n-hexane, isopentane, neopentane, benzene, toluene, methylcyclohexane or chlorinated hydrocarbons such as CH 2 Cl 2 , CH 3 Cl, C 2 H 5 Cl, chlorobenzene, ethylidene dichloride, propyl chloride, to name a few of the representative ones well known to the art.
  • Mixed solvents can also be used.
  • the mixing sequence of the ingredients may be done without regard to sequence.
  • the polymerization starts upon the introduction of the last needed ingredient when the temperature is maintained below the decomposition temperature of the complex which generally is below minus 10° C. but in some cases may be above 40° C.
  • Bulk polymerization i.e., in the absence of a solvent, can also be carried out.
  • the polymerization generally, can be carried out continuously by mixing two streams of chemicals, ester and BCl 3 preferably mixed with monomer in appropriate solvents, or ester and monomer mixed with BCl 3 or related Lewis acid at a temperature below the decomposition temperature of the complex formed.
  • the polymerization can be carried out above the decomposition temperature of the complex provided certain precautions are taken, to give savings in refrigeration costs and thus achieve economy in production.
  • These precautions in one embodiment call for the complex of an organic acid or ester with a Lewis acid to be formed below the decomposition temperature of the complex and be maintained below such temperature until their use to initiate the polymerization.
  • the reaction can also be carried out by mixing the monomer and initiator, and then introducing the Lewis acid, at a temperature that is higher than the decomposition temperature of the initiating complex.
  • These complexes may have its molecular weight increased by addition of the olefin monomers thereto, either alone, in combination, or in series, at a temperature below or above the complexes decomposition temperature provided the temperature at which the addition or polymerization of the olefin occurs is such that the rate of decomposition of the complex is low so that the decomposition of the complex does not prevent or occur before the polymerization of the olefin.
  • the premade or in situ made complex of an organic acid or ester and a Lewis acid at a temperature where the half life of the complex is about 5 minutes to an hour or more is mixed with the olefin monomer or monomers with or without suitable solvents at a temperature where the polymerization rate preferably is sufficient to substantially complete the polymerization prior to decomposition of a sufficient amount of the complex to stop or prevent the polymerization going to the desired degree of completion.
  • the premix of the ester and monomer is made and then mixed with the Lewis acid or, in some cases, mixture of Lewis acid can form the complex essentially instaneously and thus initiate monomer polymerization and complete said polymerization prior to decomposition of the complex to prevent formation of polymer of the desired molecular weight.
  • any of the complexes set forth herein or made according to the teachings hereof could be made at a temperature below its decomposition temperature, for instance about minus 10° C. to minus 40° C., preferably in a hydrocarbon or chlorohydrocarbon solvent at a very high concentration, viz., a catalyst concentrate.
  • this premade complex is added with mixing to a suitable reactor that contains the olefin monomer at a temperature of about 10° to 50° C., where the complex effects polymerization of the olefin in the mixture at a temperature preferably of about 10° to 50° prior to decomposition of sufficient complex to stop the polymerization prior to obtaining a polymer of the desired molecular weight.
  • the premade complex made below its decomposition temperature simultaneously is charged and mixed with the monomer to give a mixture above the decomposition temperature of the complex, and the mixing is controlled to give a temperature where the rate of decomposition of the complex is sufficiently so low that the undecomposed complex effects sufficient polymerization of the monomer to give the desired polymer of the desired molecular weight. It being understood that when sufficient amount of the complex has decomposed, the reaction stops.
  • the polymerization most likely occurs by the opening of the ester bond and monomer insertion, as illustrated by the following schematic and illustrative equation: ##STR5## Using the last formula in the above equation, we will exemplify the monomer insertion in the following schematic equation: ##STR6##
  • the complex counter anion is supernonnucleophilic, i.e., it does not assist or cause proton elimination from the carbocation. This is a very important characteristic that distinguishes our counter anions from other known nonnucleophilic counter anions, e.g., BCl 4 .sup. ⁇ , BF 4 .sup. ⁇ , and AlCl 4 .sup. ⁇ .
  • the complex anion of our invention is supernonnucleophilic and as such does not assist or cause deprotonation of the growing carbocationic center.
  • chain transfer to monomer will not occur in our systems, and consequently molecular weight control can be accomplished by adjusting the relative concentrations of monomer and initiating system, i.e., molecular weight is a function of [M]o/[I]o, where the subscripts include initial concentrations.
  • the polymer will grow as long as monomer is available and the monomer is not prevented from reacting with the growing center, for example, by the growing center being coagulated from the system or decomposition of sufficient [I]o to stop the polymerization.
  • the polymerization is devoid of termination, i.e., the polymerization is relatively terminationless until the temperature exceeds the decomposition temperature of the complex for sufficient time to reduce the [I]o to zero.
  • the growing center is kept “alive” for extended periods of time without losing its propogating ability.
  • termination occurs most likely by a reaction between the growing cation and associated counter anion, for example as set forth hereinafter: ##STR10##
  • the BF 3 complex yields acetate end groups under the same conditions by decomposition of the catalyst complex.
  • the acetate end group is a valuable function, and its production yields a new composition of matter having valuable properties. For instance, it can be hydrolyzed to the alcohol end group to produce another new composition as illustrated by the following equation: ##STR12##
  • Any of the well known olefin-based monomers may be used in this invention to produce polymers.
  • the alpha-olefins having usually from 2 to about 20 and preferably 4 to 8 carbon atoms may be used alone or in conjunction with themselves with a diolefin, either conjugated or nonconjugated, to produce polymers or copolymers of varying molecular weight even as low as 300 to in excess of a million.
  • These polymers can be low molecular weight liquid or viscous polymers of about 200 or 500 to 10,000 molecular weight units or the solid waxy to plastic or elastomeric materials of greater than 100,000 to 500,000 to a million or more molecular weight units.
  • these olefins are those having 2 to 20 or more carbon atoms and are readily available as specific species such as ethylene, propylene, butylene, amylenes, hexylenes, heptylenes, octylenes, the styrenes, alpha-methyl styrenes, or the dienes either nonconjugated or conjugated such as butadiene, isoprene, piperylene, hexadienes and the octadienes, and the cyclic analogues of these such as 1,3-cyclohexadiene, to name a few of the well known and representative members.
  • Examples of the Lewis acids useful in this invention are BCl 3 , BF 3 , AlCl 3 , SnCl 4 , TiCl 4 , SbF 5 , FeCl 3 and ZnCl 2 .
  • BCl 3 and BF 3 are the preferred species, the other halogens and the Lewis acids also can be used by replacing one member for another one.
  • Any of the organic acids and esters may be used provided they form a stable complex with the Lewis acids at a suitable polymerization temperature usually about minus 40° C. up to about 10° to 20° C., or if the rate of decomposition of the complex at higher temperatures is lower than the rate of polymerization.
  • the organic acids can be monocarboxylic acids, such as formic, acetic, and their homologues, say from 1 to 20 carbon atoms, with those less than 6 carbon atoms being preferred.
  • the di- and tricarboxylic acids and higher can also be used.
  • the mono-, di- and trifunctional acids offer a means of making polymers having certain specific mono-, di- or tri- end group functions such as chloride, formate, allylic, acrylic or methacrylic.
  • test tube runs were made by charging each test tube with solvent, monomer, viz., isobutylene, sometimes abbreviated as IB herein, and an initiator.
  • the polymerization was started by the addition of BCl 3 with or without solvent being present with the temperature being as given.
  • concentrations and results of these runs are given in Tables I through XII, according to the experimental run listed.
  • the polymerization was, in most cases, very rapid, i.e., the conversions reached their final values within a few minutes. Nevertheless, to be sure that the reactions did proceed to completion, the polymerization time was extended to 30 minutes. After this time, the reactions were quenched by the addition of 3.0 ml of prechilled methanol.
  • the polymer was recovered by a conventional workup, i.e., evaporation of volatiles, dissolution in n-hexane, decantation or filtration of inorganic residues such as boron compounds or the other Lewis acid residues, removal of hexane by evaporation at room temperature, etc.
  • the fact that the products were not washed insured complete product recovery; i.e., no loss of low molecular weight components.
  • the polymer products were characterized by a variety of techniques including IR, 1 H and 13 C NMR spectroscopy, osmometry and GPC with dual detection with infrared and ultraviolet.
  • tert.-butyl acetate is an efficient initiator, molecular weight control can be readily achieved by controlling the [M]o and [I]o, and chain transfer to monomer is absent even at 0° C. Since chain transfer to monomer did not occur at the relatively high temperature of 0° C., this reaction is also absent in runs carried out at lower temperatures, as indicated by 1 H NMR spectroscopy. Further, based on a variety of analytical techniques (IR, 1 H NMR, GPC), the polymers contain a tert.-butyl head group and a tert.-chlorine tail group, as shown by the following formula: ##STR13## using isobutylene as the monomer.
  • this method provides a method to produce polymers where the polyolefin segment can be any olefin segment such as polyisobutylene or PIB, polypentene, polyhexene, polyheptene, polyoctene, polystyrene, poly-alpha-methylstyrene, to name a few of the more common olefin monomer segments, or mixtures of these alpha-olefins or other alpha-olefins.
  • olefin segment such as polyisobutylene or PIB, polypentene, polyhexene, polyheptene, polyoctene, polystyrene, poly-alpha-methylstyrene, to name a few of the more common olefin monomer segments, or mixtures of these alpha-olefins or other alpha-olefins.
  • 2,5-Dimethyl-2,5-hexane diol diacetate is an initiator in conjunction with BCl 3 for the polymerization of IB, and molecular weight control is possible.
  • the polymer produced has the following structure. ##STR16## This composition has fully aliphatic telechelic end groups whereas the prior art telechelic polymers contained partial aromatic end groups. Again, this method provides a method to produce the above polymers where the PIB segment can be a polyolefin segment.
  • composition of the PIB segment would be replaced with polyolefin segments, such as blocks of aliphatic olefins of about 2 to 20 carbon atoms and conjugated diolefin segments of 4 to 12 carbon atoms.
  • the structure of this new polymer is as follows: ##STR17##
  • the PIB segment can be any polyolefin segment such as polystyrene, polyoctene, and polypropylene by changing the monomer to the desired one; say, styrene for example or octadecene.
  • the polyolefin segment can be homopolymeric, copolymers of different olefins of either aliphatic, cycloaliphatic or aryl in nature.
  • polymers having the following structure can be made which have a formate end group: ##STR19##
  • the initiator is a di- or trifunctional formate ester
  • di- and triformate terminated polyolefins are produced.
  • homo- and copolymers having formate terminal groups are produced where R 1 and R 2 have values given hereinbefore.
  • the initiator was an unsaturated formate, specifically allyl formate.
  • the polymerization conditions and results of the runs are listed in Table IX.
  • the premixing of TMPOAc and BCl 3 technique is advantageous as it produces narrower molecular weight distribution polymer than the TMPOAc and monomer and BCl 3 addition sequence. This effect can be seen by inspecting the M w /M n columns. The M w /M n values are lower in the experiment with TMPOAc and BCl 3 premixing.
  • a special embodiment of this invention relates to the random copolymerization of an alphaolefin such as those exemplified by isobutylene, propylene, pentene or hexene, with a diolefin, preferably a conjugated one such as those exemplified by isoprene, butadiene and piperylene.
  • an alphaolefin such as those exemplified by isobutylene, propylene, pentene or hexene
  • a diolefin preferably a conjugated one such as those exemplified by isoprene, butadiene and piperylene.
  • the random polymers produced by this invention have commercial utility as butyl rubbers and especially those having a molecular weight of a hundred thousand and 1 to 4 percent unsaturation.
  • These rubbers are sulfurvulcanizable, heat stable, chemically resistant general purpose rubbers which may be used in inner tubes and inner liners of tires, tubes, curing bladders, mountings, vibration dampers, etc., and are convertible to the halogenated form of butyl rubber for other usages.
  • butyl rubber was made commercially by a heterogeneous low temperature (minus 100° C.) cationic suspension polymerization by the use of AlCl 3 catalyst in methyl chloride diluent.
  • Example 14 copolymerization of isobutylene with isoprene was demonstrated to occur readily with our complex catalyst, and that the copolymerization yields random copolymers whose overall composition can be controlled by the isobutylene/isoprene ratio in that charge, and that the molecular weight of the butyl rubber formed can be controlled by the ratio of [monomers]/[initiating complex], and that the copolymerization is living in nature.
  • the percent unsaturation can be controlled over a wide molecular weight range to yield new copolymers of alpha-olefins and dienes which may have higher molecular weights, i.e., in excess of a hundred thousand molecular weight and having unsaturation values of 1, 2, 3 to 5 mole percent and higher.
  • copolymers having 1 to 90 and preferably 2 to 10 percent of diolefin are readily made.
  • a series of copolymerization experiments have been carried out under the following conditions: A series of three test tubes have been charged at minus 30° C. with 22.5 ml CH 3 Cl, 2.0 ml isobutylene (0.94 mole/l) and 0.1 ml cumyl acetate (0.56 ⁇ 10 -3 mole/l) in that order. Then in a series of three test tubes, isoprene was introduced, i.e., 0.05 ml (or 2.13 mole percent on isobutylene); 0.1 ml (or 4.26 mole percent on isobutylene); and 0.2 ml (or 8.52 mole percent on isobutylene) isoprene.
  • the second series of copolymerizations have been carried out with 2.13 mole percent isoprene (on isobutylene) in the charge. Copolymerizations were terminated after 5 and 10 minutes after BCl 3 addition. In the third tube at 20 minutes, we added a fresh charge of 2.05 ml monomer mixture consisting of 2.0 ml isobutylene and 0.05 ml isoprene, i.e., a charge of 2.13 mole percent isoprene (on isobutylene), and allowed the reaction to proceed for an additional 30 minutes. After killing and workup, the conversion and the molecular weight of the polymers were determined. Table XVb and FIG. 5 show the results.
  • the copolymerizations proceeded in a living manner as indicated by the linear M n versus conversion plots crossing the origin.
  • the polymerizations described in this invention can be carried out as long as the initiating complex maintains its integrity to give a wide range of molecular weights. Tests determined that the tert.-butyl acetate BCl 3 complex is stable up until at least minus 10° C. Therefore, living and other polymerization can be carried out up to at least minus 10° C. and even to the decomposition temperature of the complex which in most cases is near ambient or 10°-30° C. below it, but some initiator complexes allows operating tempertures above 0° C. Thus, butyl rubber can be made at much higher temperatures than heretofore.
  • t-BuAC 0.06 ml tert.-butyl acetate
  • BCl 3 0.06 ml BCl 3
  • the TMPOAc.BCl 3 complex is stable up until minus 10° C. but it decomposes quantitatively at room temperature to TMP-Cl and CH 3 COCl, upon standing at this temperature for sufficient time.
  • tert.-chloride groups can be quantitatively obtained not only by treating the polymerizing system to bring it to room temperature, but also by adding various nucleophilic killing or quenching agents, i.e., CH 3 OH, (C 2 H 5 ) 3 N, pyridine, ammonia, methanol, and sodium methoxide.
  • nucleophilic killing or quenching agents i.e., CH 3 OH, (C 2 H 5 ) 3 N, pyridine, ammonia, methanol, and sodium methoxide.
  • R 2 is the same as R 1 ;
  • R 3 is the same as R 2 ;
  • R 4 is methylene or polymethylene, ethylenic, acetylenic, ##STR24## or related homologous groups;
  • R 8 is a trivalent organic moiety;
  • y is hydrogen or alkyl

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Abstract

This invention provides a novel catalyst composed of a complex of an organic acid or its ester and a Lewis acid, preferably boron trichloride that can add olefin monomers to increase the molecular weight of the complex from as low as 200 to in excess of a million, with the complex being active viz., living, until the complex dies, viz., is decomposed or destroyed so that polymers in the liquid or easily liquefiable range of 300 to about 20,000 can be made or those more difficult to be liquefied or unliquefiable, viz., those of over 10,000 up to 100,000 or in some cases 500,000 and then those in the range of the elastomers, or moldable or extrudable plastics range having very high molecular weights, generally in excess of 100,000 up to in excess of 500,000 and having useful end groups such as the halogens and specifically chloride, allyl, acryl or methacryl, acetate or formate to name some of the more useful ones.

Description

This application is a continuation-in-part of application Ser. No. 746,835 filed June 20, 1985 now abandoned.
TECHNICAL FIELD
This invention relates to a novel class of complexes, useful as living polymerization catalysts to produce novel polymers having specific end groups and especially new type polymers such as butyl rubber and related polymers. More particularly, this invention relates to novel complex compounds containing or incorporating at least one or a number of olefinic monomers but sufficient to give a range of molecular weights from the very low range of about 200, 500 or 10,000 to the extremely high range of 500,000 or a million and higher. Specifically, this invention provides a so-called living polymer preparation method that allows polymers to be made as homopolymers, random copolymers, to highly specialized block copolymers, or terpolymers, and the like.
BACKGROUND ART
Truly living polymerization, i.e., truly terminationless and chain transferless polymerizations, are a most desirable objective of the synthetic polymer chemist. If the rates of both termination and chain transfer are zero, Rt =Rtr =0, and the rate of initiation is larger than that of propagation Ri >Rp, polymer molecule weights are determined by the ratio [M]/[I] (i.e., monomer over initiator concentrations) and Mw /Mn will be reasonably small. If Ri is instantaneous and/or Ri >>Rp, then Mw /Mn ˜1.0. Living polymerizations are not only of scientific interest, but also of great commercial consequence, and several industrial processes are based on living systems, e.g., cis-1,4-polybutadiene, triblock copolymers of styrene/butadiene/styrene, polytetrahydrofuran, but these are not carbocationic polymerization processes.
Although great efforts have been made to develop living carbocationic polymerizations, success remains rather limited. The only truly living carbocationic systems described to date are those achieved by Higashimura, Sawamoto, et al. involving the HI/I2 initiator system and the highly cationically reactive monomers such as vinyl ethers, p-methoxy styrene and N-vinyl carbazole. Under certain well-defined experimental conditions, quasiliving carbocationic polymerizations approach those of truly living polymerizations but only under quite restrictive conditions, i.e., very low temperatures, continuous slow monomer addition (when the rate of monomer addition and that of monomers consumption are equal), and even then the rate of chain transfer is not exactly zero, but only approaches zero. Also, in quasiliving polymerizations, Rt is not zero, but termination is reversible so that over a reasonably long time period termination appears to be absent, hence the term "quasiliving."
DISCLOSURE OF INVENTION
Recently, we have developed a series of new initiator systems that lead us to truly living polymerization systems for olefins such as isobutylene, copolymerization systems of an olefin such as isobutylene with a diolefin such as isoprene, and to new telechelic end reactive polymers of isobutylene or related olefins.
This invention concerns a new family of initiating systems, a new process for making polymers and a series of new products having specific end groups thereon.
The family of initiating systems is based on organic acids or esters in conjunction with a Lewis acid, preferably BCl3, as illustrated by the following formulae: ##STR1## where R1 in the above formula may be H, halogen, an organic moiety such as methyl and related alkyl, or aryl groups, preferably up to about 14 to 20 carbon atoms, alkylene groups such as --CH═CH2 and related lower alkylene groups, preferably 2 to about 8 carbon atoms, and groups containing hetero atoms and related groups such as alkylene chloride, methylene to butylene alkoxy, preferably up to about 14 to 20 carbon atoms;
R2 may be H, methyl and related alkyl groups containing preferably from 1 to about 14 to 20 carbon atoms, in general R2 can be the same as R1 ;
R3 may be methyl, or related alkyls of preferably 2 to about 20 carbon atoms or aryls such as phenyl, cycloalkyls, or vinyl or allyl groups or a CH2 ═group, in general R3 can be the same as R2 ;
R4 may be (CH2)x, or other moiety such as --CH2 --CH2 --, acetylenic such as --C.tbd.C--, or arylene such as ##STR2## or ethylenic such as --CH═CH-- and related homologous groups; where x is 1 to about 20 and preferably 1 to 10 in value;
R5 may be alkylenes such as --CH2 --, and substituted alkylenes such as ##STR3## or other well known groups where H and methyl have been replaced to produce the related homologous series that yield many lactones having alkyl, aryl, alkaryl, arylalkyl and cycloalkyl groups substituted on the carbon in the lactone ring;
R6 may be the same as R1 but preferably limited to H or alkyls such as methyl or ethyl or aryl; and
R7 is an alkylene group containing carbon atoms to complete the lactone ring over the range of 3 to about 20 carbon atoms or more or an alkylene group having the hydrogen atoms on at least one of the carbon atoms substituted with other carbon atoms or customary carbon atoms substituents;
R8 may be a three valent organic moiety such as ##STR4##
It should be appreciated that R2 in the above formulae can be the same or different.
BEST MODE FOR CARRYING OUT THE INVENTION
The polymerization can be carried out at an appropriate temperature by contacting preferably in a liquid diluent the olefinic monomer or monomers, the organic acid or ester and BCl3 or related Lewis acid. The diluents preferably are hydrocarbons such as n-butane, n-pentane, n-hexane, isopentane, neopentane, benzene, toluene, methylcyclohexane or chlorinated hydrocarbons such as CH2 Cl2, CH3 Cl, C2 H5 Cl, chlorobenzene, ethylidene dichloride, propyl chloride, to name a few of the representative ones well known to the art. Mixed solvents can also be used.
As to the mixing sequence of the ingredients, they may be done without regard to sequence. For example, one can premix the organic ester and BCl3 in a solvent and then add the monomer in a solvent and then add the BCl3 in a solvent. Generally, the polymerization starts upon the introduction of the last needed ingredient when the temperature is maintained below the decomposition temperature of the complex which generally is below minus 10° C. but in some cases may be above 40° C. Bulk polymerization, i.e., in the absence of a solvent, can also be carried out.
The polymerization, generally, can be carried out continuously by mixing two streams of chemicals, ester and BCl3 preferably mixed with monomer in appropriate solvents, or ester and monomer mixed with BCl3 or related Lewis acid at a temperature below the decomposition temperature of the complex formed.
In a special embodiment, we also have discovered that the polymerization can be carried out above the decomposition temperature of the complex provided certain precautions are taken, to give savings in refrigeration costs and thus achieve economy in production. These precautions in one embodiment call for the complex of an organic acid or ester with a Lewis acid to be formed below the decomposition temperature of the complex and be maintained below such temperature until their use to initiate the polymerization.
Since the formation of the initiating organic acid or ester-Lewis acid complex is instantaneous, in another embodiment, the reaction can also be carried out by mixing the monomer and initiator, and then introducing the Lewis acid, at a temperature that is higher than the decomposition temperature of the initiating complex. These complexes may have its molecular weight increased by addition of the olefin monomers thereto, either alone, in combination, or in series, at a temperature below or above the complexes decomposition temperature provided the temperature at which the addition or polymerization of the olefin occurs is such that the rate of decomposition of the complex is low so that the decomposition of the complex does not prevent or occur before the polymerization of the olefin.
In this special embodiment, the premade or in situ made complex of an organic acid or ester and a Lewis acid at a temperature where the half life of the complex is about 5 minutes to an hour or more is mixed with the olefin monomer or monomers with or without suitable solvents at a temperature where the polymerization rate preferably is sufficient to substantially complete the polymerization prior to decomposition of a sufficient amount of the complex to stop or prevent the polymerization going to the desired degree of completion. For instance, the premix of the ester and monomer is made and then mixed with the Lewis acid or, in some cases, mixture of Lewis acid can form the complex essentially instaneously and thus initiate monomer polymerization and complete said polymerization prior to decomposition of the complex to prevent formation of polymer of the desired molecular weight.
To specifically illustrate this special embodiment, any of the complexes set forth herein or made according to the teachings hereof, could be made at a temperature below its decomposition temperature, for instance about minus 10° C. to minus 40° C., preferably in a hydrocarbon or chlorohydrocarbon solvent at a very high concentration, viz., a catalyst concentrate. Then, this premade complex is added with mixing to a suitable reactor that contains the olefin monomer at a temperature of about 10° to 50° C., where the complex effects polymerization of the olefin in the mixture at a temperature preferably of about 10° to 50° prior to decomposition of sufficient complex to stop the polymerization prior to obtaining a polymer of the desired molecular weight.
In another embodiment, the premade complex made below its decomposition temperature simultaneously is charged and mixed with the monomer to give a mixture above the decomposition temperature of the complex, and the mixing is controlled to give a temperature where the rate of decomposition of the complex is sufficiently so low that the undecomposed complex effects sufficient polymerization of the monomer to give the desired polymer of the desired molecular weight. It being understood that when sufficient amount of the complex has decomposed, the reaction stops. Thus, we have discovered that polymerization under these special embodiment conditions can be practiced because the rates of polymerizations are relatively fast, usually being complete in a manner of one to three minutes and in nearly all cases, in a matter of 30 minutes while the rate of decomposition is such to give a half life of about 5 minutes to an hour at temperatures of about 20° C. to 30° C. Therefore, not only homopolymers but copolymers and block polymers can be made above the decomposition temperature of the complex when these precautions are taken.
The polymerization most likely occurs by the opening of the ester bond and monomer insertion, as illustrated by the following schematic and illustrative equation: ##STR5## Using the last formula in the above equation, we will exemplify the monomer insertion in the following schematic equation: ##STR6## The complex counter anion is supernonnucleophilic, i.e., it does not assist or cause proton elimination from the carbocation. This is a very important characteristic that distinguishes our counter anions from other known nonnucleophilic counter anions, e.g., BCl4.sup.⊖, BF4.sup.⊖, and AlCl4.sup.⊖. In conventional polymerizations taking place in the presence of simple nonnucleophilic counter anions, the latter assists or causes proton elimination from the growing carbocationic center and thus a species arises that proceeds to protonate monomer. For example, with BF4.sup.⊖ counter anion: ##STR7## the latter protonates incoming monomer as follows: ##STR8## This sequence of events constitutes chain transfer to monomer and it is a most undesirable process for polymer chemists. First of all, this process reduces the molecular weight of the polymer that is formed, and secondly it yields polymers carrying an undesirable unreactive head-group ##STR9## Molecular weight control in systems that involve chain transfer to monomer is more difficult to achieve than in systems devoid of this process. Thus, an advantage of our invention is it avoids the above two shortcomings.
The complex anion of our invention is supernonnucleophilic and as such does not assist or cause deprotonation of the growing carbocationic center. Thus, chain transfer to monomer will not occur in our systems, and consequently molecular weight control can be accomplished by adjusting the relative concentrations of monomer and initiating system, i.e., molecular weight is a function of [M]o/[I]o, where the subscripts include initial concentrations. The polymer will grow as long as monomer is available and the monomer is not prevented from reacting with the growing center, for example, by the growing center being coagulated from the system or decomposition of sufficient [I]o to stop the polymerization.
Also on account of the supernonnucleophilic nature of our counter anions, the polymerization is devoid of termination, i.e., the polymerization is relatively terminationless until the temperature exceeds the decomposition temperature of the complex for sufficient time to reduce the [I]o to zero. The growing center is kept "alive" for extended periods of time without losing its propogating ability. In contrast, in conventional polymerization termination occurs most likely by a reaction between the growing cation and associated counter anion, for example as set forth hereinafter: ##STR10##
While uninterrupted growth can be maintained for extended periods of time with systems containing supernonnucleophilic counter anions, if termination is desired, say for the preparation of low molecular weight end-functionalyzed polymer, such a premature termination reaction can be brought about by either increasing the temperature of the polymerization system and thus decomposing the active growing complex, or by adding a strong nucleophilic terminating agent, such as methanol or ethanol, pyridine, ammonia, an alkyl amine, or water. Thus, our invention provides a mechanism of varying the molecular weight from several hundreds to the millions. These reactions may result in a Cl-terminated polymer (or a halogen-terminated polymer) most likely because of the following termination reaction: ##STR11## The concurrently formed BCl2 ester is unstable and is converted to other products. The tert.-chloride end group is a valuable end function and can be used in a variety of well known applications.
The BF3 complex yields acetate end groups under the same conditions by decomposition of the catalyst complex. The acetate end group is a valuable function, and its production yields a new composition of matter having valuable properties. For instance, it can be hydrolyzed to the alcohol end group to produce another new composition as illustrated by the following equation: ##STR12## Any of the well known olefin-based monomers may be used in this invention to produce polymers. The alpha-olefins having usually from 2 to about 20 and preferably 4 to 8 carbon atoms may be used alone or in conjunction with themselves with a diolefin, either conjugated or nonconjugated, to produce polymers or copolymers of varying molecular weight even as low as 300 to in excess of a million. These polymers can be low molecular weight liquid or viscous polymers of about 200 or 500 to 10,000 molecular weight units or the solid waxy to plastic or elastomeric materials of greater than 100,000 to 500,000 to a million or more molecular weight units. Examples of these olefins are those having 2 to 20 or more carbon atoms and are readily available as specific species such as ethylene, propylene, butylene, amylenes, hexylenes, heptylenes, octylenes, the styrenes, alpha-methyl styrenes, or the dienes either nonconjugated or conjugated such as butadiene, isoprene, piperylene, hexadienes and the octadienes, and the cyclic analogues of these such as 1,3-cyclohexadiene, to name a few of the well known and representative members.
Examples of the Lewis acids useful in this invention are BCl3, BF3, AlCl3, SnCl4, TiCl4, SbF5, FeCl3 and ZnCl2. Although BCl3 and BF3 are the preferred species, the other halogens and the Lewis acids also can be used by replacing one member for another one. Any of the organic acids and esters may be used provided they form a stable complex with the Lewis acids at a suitable polymerization temperature usually about minus 40° C. up to about 10° to 20° C., or if the rate of decomposition of the complex at higher temperatures is lower than the rate of polymerization. Also, the organic acids can be monocarboxylic acids, such as formic, acetic, and their homologues, say from 1 to 20 carbon atoms, with those less than 6 carbon atoms being preferred. The di- and tricarboxylic acids and higher can also be used. The mono-, di- and trifunctional acids offer a means of making polymers having certain specific mono-, di- or tri- end group functions such as chloride, formate, allylic, acrylic or methacrylic.
The nature of this invention and its many aspects and advantages may be more readily understood and appreciated by reference to the following representative and illustrative examples.
The general polymerization process used in Examples 1 to 11 was as follows:
A series of test tube runs were made by charging each test tube with solvent, monomer, viz., isobutylene, sometimes abbreviated as IB herein, and an initiator. The polymerization was started by the addition of BCl3 with or without solvent being present with the temperature being as given. The concentrations and results of these runs are given in Tables I through XII, according to the experimental run listed. The polymerization was, in most cases, very rapid, i.e., the conversions reached their final values within a few minutes. Nevertheless, to be sure that the reactions did proceed to completion, the polymerization time was extended to 30 minutes. After this time, the reactions were quenched by the addition of 3.0 ml of prechilled methanol. The polymer was recovered by a conventional workup, i.e., evaporation of volatiles, dissolution in n-hexane, decantation or filtration of inorganic residues such as boron compounds or the other Lewis acid residues, removal of hexane by evaporation at room temperature, etc. The fact that the products were not washed insured complete product recovery; i.e., no loss of low molecular weight components. The polymer products were characterized by a variety of techniques including IR, 1 H and 13 C NMR spectroscopy, osmometry and GPC with dual detection with infrared and ultraviolet.
EXAMPLE 1
A series of experiments were made using tert.-butyl acetate as the initiator. The results of the individual experiments, a total of 23 runs, are shown in Table I, together with the conditions (concentration of chemicals, temperatures, etc.) used.
According to the data, tert.-butyl acetate is an efficient initiator, molecular weight control can be readily achieved by controlling the [M]o and [I]o, and chain transfer to monomer is absent even at 0° C. Since chain transfer to monomer did not occur at the relatively high temperature of 0° C., this reaction is also absent in runs carried out at lower temperatures, as indicated by 1 H NMR spectroscopy. Further, based on a variety of analytical techniques (IR, 1 H NMR, GPC), the polymers contain a tert.-butyl head group and a tert.-chlorine tail group, as shown by the following formula: ##STR13## using isobutylene as the monomer.
                                  TABLE I                                 
__________________________________________________________________________
Monomer:          isobutylene [M] = 1 mol/l                               
Initiator:        tert.-butylacetate [I] = as stated, mol/l               
Coinitiator:      BCl.sub.3 [BCl.sub.3 ] = 2.6 × 10.sup.-1 mol/l    
Solvent:          as stated                                               
Polymeriza-                                                               
tion Time:        30 minutes, unless stated otherwise                     
Run                   Conversion                                          
Number                                                                    
     Temp. °C.                                                     
           Solvent                                                        
                [I]   Percent                                             
                            --M.sub.n                                     
                                 --M.sub.w                                
                                     --M.sub.w /--M.sub.n                 
__________________________________________________________________________
1a              2.8 × 10.sup.-2                                     
                      74.5* 6000 9400                                     
                                     1.6                                  
1b   -50° C.                                                       
           CH.sub.3 Cl                                                    
                2.8 × 10.sup.-2                                     
                      100*  7370 15000                                    
                                     2.0                                  
1c              5.6 × 10.sup.-2                                     
                      100   4240 7210                                     
                                     1.7                                  
1d              5.6 × 10.sup.-2                                     
                      100   4340 7420                                     
                                     1.7                                  
1e              5.6 × 10.sup.-3                                     
                      9.4   27400                                         
                                 48800                                    
                                     1.8                                  
1f              5.6 × 10.sup.-3                                     
                      13.5  31000                                         
                                 48200                                    
                                     1.5                                  
1g              5.6 ×  10.sup.-3                                    
                      55.0**                                              
                            22000                                         
                                 39000                                    
                                     1.8                                  
1h              2.8 × 10.sup.-2                                     
                      43.5  5480 10200                                    
                                     1.8                                  
1i   -30° C.                                                       
           CH.sub.3 Cl                                                    
                2.8 × 10.sup.-2                                     
                      87.5  4130 8400                                     
                                     2.0                                  
1j              2.8 × 10.sup.-2                                     
                      100   4650 8930                                     
                                     1.9                                  
1k              5.6 × 10.sup.-2                                     
                      100   2950***                                       
                                 5590                                     
                                     1.9                                  
1l              5.6 × 10.sup.-2                                     
                      100   3360***                                       
                                 6290                                     
                                     1.9                                  
1m              5.6 × 10.sup.-2                                     
                      100   3200***                                       
                                 6200                                     
                                     1.9                                  
1n              5.6 × 10.sup.-2                                     
                      100   2750***                                       
                                 5600                                     
                                     2.0                                  
1o              5.6 × 10.sup.-3                                     
                      100   27500                                         
                                 66800                                    
                                     2.4                                  
1p   -30° C.                                                       
           CH.sub.2 Cl.sub.2                                              
                2.8 × 10.sup.-2                                     
                      100   4230 10420                                    
                                     2.4                                  
1q              5.6 × 10.sup.-2                                     
                      100   2470***                                       
                                 5950                                     
                                     2.4                                  
1r   -20° C.                                                       
           CH.sub.2 Cl.sub.2                                              
                2.8 × 10.sup.-2                                     
                      100   5940 10700                                    
                                     1.8                                  
1s              5.6 × 10.sup.-2                                     
                      100   2260***                                       
                                 6900                                     
                                     3.0                                  
1t   -10° C.                                                       
           CH.sub.2 Cl.sub.2                                              
                2.8 × 10.sup.-2                                     
                      100   4370 9200                                     
                                     2.1                                  
1u              5.6 × 10.sup.-2                                     
                      100   2040***                                       
                                 5090                                     
                                     2.5                                  
1v   0° C.                                                         
           CH.sub.2 Cl.sub.2                                              
                2.8 × 10.sup.-2                                     
                      100   4000 8100                                     
                                     2.0                                  
1w              5.6 × 10.sup.-2                                     
                      100   2100***                                       
                                 4560                                     
                                     2.2                                  
__________________________________________________________________________
 *In these experimental runs, the polymerization time was 1 hour          
 **In these experimental runs, the polymerization time was 100 minutes    
 ***Examination of the polymer showed the absence of terminal unsaturation
 in the product indicating the absence of chain transfer to the monomer.  

                                  TABLE II                                
__________________________________________________________________________
Monomer:          isobutylene, [M] = 1 mol/l                              
Initiator:        2,4,4-trimethylpenty-2-acetate [I] = as stated          
Coinitiator:      BCl.sub.3 = 2.6 10.sup.-2 mol/l                         
Solvent:          as stated                                               
Temperature:      as stated                                               
Polmeriza-                                                                
tion Time:        30 minutes                                              
Run                                                                       
Number                                                                    
     Temp. °C.                                                     
           Solvent                                                        
                 [I]   Conversion %                                       
                               --M.sub.n                                  
                                   --M.sub.w                              
                                       --M.sub.w /--M.sub.n               
__________________________________________________________________________
2a               5.6 × 10.sup.-3                                    
                       100     10500                                      
                                   21500                                  
                                       2.0                                
2b   -50° C.                                                       
           CH.sub.3 Cl                                                    
                 2.8 × 10.sup.-2                                    
                       100     1800                                       
                                   6300                                   
                                       3.6                                
2c               5.6 × 10.sup.-2                                    
                       100     1400                                       
                                   3400                                   
                                       2.4                                
2d               5.6 × 10.sup.-3                                    
                       100     10770                                      
                                   15750                                  
                                       1.46                               
2e   -30° C.                                                       
           CH.sub.3 Cl                                                    
                 2.8 × 10.sup.-2                                    
                       100     2090                                       
                                   5320                                   
                                       2.5                                
2f               2.8 × 10.sup.-2                                    
                       100     2200                                       
                                   5650                                   
                                       2.5                                
2g               5.6 × 10.sup.-2                                    
                       100     1290                                       
                                   2800                                   
                                       2.2                                
2h   -30° C.                                                       
           CH.sub.3 Cl/n-                                                 
           hexane                                                         
                 2.8 × 10.sup.-2                                    
                       100     2260                                       
                                   3150                                   
                                       1.39                               
           (60:40)                                                        
__________________________________________________________________________
EXAMPLE 2
Another series of experiments were made using 2,4,4-trimethylpentyl-2-acetate as the initiator instead of the tertiary butyl acetate of Example 1. The solvent was mixed with the initiator and monomer at the temperature indicated for the various runs in Table II and then were added to the reactor, and last the BCl3 was added. The runs from 2a through 2h show the molecular weight varied from about 1,300 to in excess of 10,000.
EXAMPLE 3
The experimental conditions of Examples 1 and 2 were used in this example except the initiator was benzyl acetate and the temperature varied from minus 30° to minus 50° C. and showed that polymer was produced over the range of molecular weights from about 30,000 to 125,000 and higher. The data for these experiments 3a through 3d is shown in Table III.
Ultraviolet spectrographic analysis of the polymers of Table III indicated the phenyl ring was in the polymer. Benzyl acetate is an initiator in conjunction with BCl3 for the polymerization of an olefin such as IB, and molecular weight control is possible. These polymers are new and have the following generic structure. ##STR14##
Thus, this method provides a method to produce polymers where the polyolefin segment can be any olefin segment such as polyisobutylene or PIB, polypentene, polyhexene, polyheptene, polyoctene, polystyrene, poly-alpha-methylstyrene, to name a few of the more common olefin monomer segments, or mixtures of these alpha-olefins or other alpha-olefins.
                                  TABLE III                               
__________________________________________________________________________
Monomer:        isobutylene, [M] = 1 mol/l                                
Initiator:      benzyl acetate, [I] = as stated, mol/l                    
Coinitiator:    BCl.sub.3 [BCl.sub.3 ] = 2.6 × 10.sup.-1, mol/l     
Solvent:        CH.sub.3 Cl                                               
Polymeriza-                                                               
tion Time:      30 minutes                                                
Run  Temperature                                                          
Number                                                                    
     °C.                                                           
            [I]   Conversion %                                            
                          --M.sub.n                                       
                              --M.sub.w                                   
                                  --M.sub.w /--M.sub.n                    
__________________________________________________________________________
3a          5.6 × 10.sup.-3                                         
                  8.4     126300                                          
                              228700                                      
                                  1.8                                     
3b   -50° C.                                                       
            2.8 × 10.sup.-2                                         
                  9.4     80200                                           
                              139100                                      
                                  1.7                                     
3c          5.6 × 10.sup.-2                                         
                  12.5    66700                                           
                              115800                                      
                                  1.7                                     
3d   -30° C.                                                       
            5.6 × 10.sup.-2                                         
                  5.6     36100                                           
                              6100                                        
                                  1.7                                     
__________________________________________________________________________
EXAMPLE 4
A series of experiments were made according to the procedure of Example 1 using cumyl acetate as the initiator and the results of these experiments are reported in Table IVa, IVb, and IVc.
NMR and ultraviolet analysis of the polymer of Table IVa indicated the structure shown: ##STR15## This structure is the same structure obtained by the polymerization of IB with the known cumyl chloride inifer system.
              TABLE IV(a)                                                 
______________________________________                                    
Monomer:  isobutylene, [M] = mol/l                                        
Initiator:                                                                
          cumyl acetate, [I] = as stated, mol/l                           
Coinitiator:                                                              
          BCl.sub.3 expressed as [BCl.sub.3 ] = 2.6 × 10.sup.-1     
          mol/l                                                           
Solvent:  CH.sub.3 Cl                                                     
Polymeriza-                                                               
tion Time:                                                                
          30 minutes                                                      
Temperature:                                                              
          -30° C.                                                  
Run               Conversion                                              
Number [I]        %         --M.sub.n                                     
                                  --M.sub.w                               
                                        --M.sub.w /--M.sub.n              
______________________________________                                    
4a     5.80 × 10.sup.-4                                             
                  16.2      19300 32700 1.7                               
4b     5.84 × 10.sup.-3                                             
                  100*      8510  13600 1.6                               
4c     2.92 × 10.sup.-2                                             
                  100       2000  3400  1.7                               
4d     5.84 × 10.sup.-2                                             
                  100       1160  2820  2.4                               
______________________________________                                    
 *Conversion was 100% after 1 minute of polymerization time.              

              TABLE IV(b)                                                 
______________________________________                                    
Monomer:  isobutylene, [M] = 1 mol/l                                      
Initiator:                                                                
          cumyl acetate, [I] = as stated, mol/l                           
Coinitiator:                                                              
          BCl.sub.3 expressed as [BCl.sub.3 ] = 2.8 × 10.sup.-1     
          mol/l                                                           
Solvent:  C.sub.2 H.sub.5 Cl                                              
Polymeriza-                                                               
tion Time:                                                                
          30 minutes                                                      
Temperature:                                                              
          -30° C.                                                  
Run               Conversion                                              
Number [I]        %         --M.sub.n                                     
                                  --M.sub.w                               
                                        --M.sub.w /--M.sub.n              
______________________________________                                    
4b/a   5.6 × 10.sup.-3                                              
                   100*     9500  14100 1.48                              
4b/b   2.8 × 10.sup.-2                                              
                  100       2390  3980  1.66                              
4b/c   5.6 × 10.sup.-2                                              
                  100       1260  2050  1.6                               
______________________________________                                    
 *conversion was 100% after 1 minute polymerization time.                 

              TABLE IV(c)                                                 
______________________________________                                    
Monomer:  isobutylene, [M] = as stated, mol/l                             
Initiator:                                                                
          cumyl acetate, [I] = 5.6 × 10.sup.-3 mol/l                
Coinitiator:                                                              
          BCl.sub.3 [BCl.sub.3 ] = 2.8 × 10.sup.-1 mol/l            
Solvent:  CH.sub.2 Cl.sub.2                                               
Polymeriza-                                                               
tion Time:                                                                
          30 minutes                                                      
Temperature:                                                              
          -10° C.                                                  
Number [M]     Conversion %                                               
                           --M.sub.n                                      
                                 --M.sub.w                                
                                        --M.sub.w /--M.sub.n              
______________________________________                                    
4c/a   0.225   100         2640  5000   1.89                              
4c/b   0.45    100         5800  9900   1.7                               
4c/c   0.676   100         8200  13900  1.69                              
4c/d   0.9     100         10400 16300  1.57                              
______________________________________
EXAMPLE 5
In these experimental runs, a difunctional initiator, 2,5-dimethyl-2,5-hexane diol diacetate was used in place of the initiator of Example 4 and the polymerization temperature was lower, namely minus 50° C.
2,5-Dimethyl-2,5-hexane diol diacetate is an initiator in conjunction with BCl3 for the polymerization of IB, and molecular weight control is possible. The polymer produced has the following structure. ##STR16## This composition has fully aliphatic telechelic end groups whereas the prior art telechelic polymers contained partial aromatic end groups. Again, this method provides a method to produce the above polymers where the PIB segment can be a polyolefin segment. Thus, in the generic formula for the above fully aliphatic telechelic end groups, composition of the PIB segment would be replaced with polyolefin segments, such as blocks of aliphatic olefins of about 2 to 20 carbon atoms and conjugated diolefin segments of 4 to 12 carbon atoms.
              TABLE V                                                     
______________________________________                                    
Monomer:     isobutylene, [M] = 1 mol/l                                   
Initiator:   2,5-dimethyl-2,5-hexane diol diacetate,                      
             [I] = as stated, mol/l                                       
Coinitiator: BCl.sub.3 [BCl.sub.3 ] = 2.6 × 10.sup.-1 mol/l         
Solvent:     CH.sub.3 Cl                                                  
Pol. Time:   30 minutes                                                   
Temperature: -50° C.                                               
Run              Conversion                                               
Number [I]       %         --M.sub.n                                      
                                 --M.sub.w                                
                                        --M.sub.w /--M.sub.n              
______________________________________                                    
5a     5.6 × 10.sup.-3                                              
                 5.2       35100 60600  1.7                               
5b     2.8 × 10.sup.-2                                              
                 8.5       11100 20000  1.8                               
5c     5.6 × 10.sup.-2                                              
                 9.0        6150 12500  2.0                               
______________________________________
EXAMPLE 6
Another difunctional initiator as shown in Table VI was used in this run instead of the one used in Example 4.
Ultraviolet absorption of the polymers of Table VI indicated the presence of initiator segments, viz., triple bonds. The structure of this new polymer is as follows: ##STR17## Again, we have a fully aliphatic telechelic polymer which contains an acetylenic bond therein and the PIB segment can be any polyolefin segment such as polystyrene, polyoctene, and polypropylene by changing the monomer to the desired one; say, styrene for example or octadecene. Hence, the polyolefin segment can be homopolymeric, copolymers of different olefins of either aliphatic, cycloaliphatic or aryl in nature.
              TABLE VI                                                    
______________________________________                                    
Monomer:     isobutylene, [M] = 1 mol/l                                   
Initiator:   2,5-dimethyl-2,5-hexyne diol diacetate,                      
             [I] = as stated, mol/l                                       
Coinitiator: BCl.sub.3 [BCl.sub.3 ] = 2.6 × 10.sup.-2 mol/l         
Solvent:     CH.sub.2 Cl.sub.2                                            
Polymeriza-                                                               
tion Time:   30 minutes                                                   
Temperature: -30° C.                                               
Run                                                                       
Number [I]       Conversion %                                             
                             --M.sub.n                                    
                                  --M.sub.w                               
                                        --M.sub.w /--M.sub.n              
______________________________________                                    
6a     2.8 × 10.sup.-2                                              
                 62.2        4000 5570  1.38                              
6b     5.6 × 10.sup.-2                                              
                 66.7        3000 4140  1.38                              
______________________________________
EXAMPLE 7
A series of runs were made at minus 30° C. with acetic acid as the initiator. The results of these runs are given in Table VII.
EXAMPLE 8
A series of runs were made at various temperatures with tert.-butyl formate as the initiator. The results are given in Table VIII.
Molecular weight control is possible by controlling [M]/[complex] ratio. Ultraviolet spectroscopy analysis indicates the presence of formate end groups in the products of Table VIII. Thus, according to this finding, we have a new composition of matter having the following structure: ##STR18## which is characterized by the presence of a formate end group.
Thus, by this method, polymers having the following structure can be made which have a formate end group: ##STR19## Where the initiator is a di- or trifunctional formate ester, di- and triformate terminated polyolefins are produced. Thus, homo- and copolymers having formate terminal groups are produced where R1 and R2 have values given hereinbefore.
              TABLE VII                                                   
______________________________________                                    
Monomer:      isobutylene, [M] = 1 mol/l                                  
Initiator:    acetic acid, [I] = as stated, mol/l                         
Coinitiator:  BCl.sub.3 [BCl.sub.3 ] = 2.6 × 10.sup.-2 mol/l        
Solvent:      CH.sub.3 Cl                                                 
Polymeriza-                                                               
tion Time:    30 minutes                                                  
Temperature:  -30° C.                                              
Run              Conversion                                               
Number [I]       %         --M.sub.n                                      
                                 --M.sub.w                                
                                        --M.sub.w /--M.sub.n              
______________________________________                                    
7a     5.6 × 10.sup.-3                                              
                 100       11600 14800   1.25                             
7b     2.8 × 10.sup.-2                                              
                 100       6700  9700   1.4                               
7c     5.6 × 10.sup.-2                                              
                 100       4700  6900   1.5                               
______________________________________                                    

                                  TABLE VIII                              
__________________________________________________________________________
Monomer:     isobutylene [M] = 1 mol/l                                    
Initiator:   tert.-butyl formate [I] = as stated, mol/l                   
Coinitiator: BCl.sub.3 [BCl.sub.3 ] = 1.1 × 10.sup.-1 mol/l         
Solvent:     CH.sub.3 Cl                                                  
Polymeriza-                                                               
tion Time:   30 minutes                                                   
Temperature: as stated                                                    
Run              Conversion                                               
Number                                                                    
     Temp. °C.                                                     
           [I]   Percent                                                  
                       --M.sub.n                                          
                           --M.sub.w                                      
                               --M.sub.w --M.sub.n                        
__________________________________________________________________________
8a         5.6 × 10.sup.-3                                          
                 100   9200                                               
                           79000                                          
                               8.6                                        
8b   -30° C.                                                       
           2.8 × 10.sup.-2                                          
                 100   1700                                               
                           10000                                          
                               6.0                                        
8c         5.6 × 10.sup.-2                                          
                 100   900 5100                                           
                               5.9                                        
8d         2.8 × 10.sup.-4                                          
                 63.0  109700                                             
                           211000                                         
                               1.9                                        
8e         5.6 × 10.sup.-4                                          
                 78.1  66400                                              
                           157000                                         
                               2.4                                        
8f   -40° C.                                                       
           1.4 × 10.sup.-3                                          
                 100   40500                                              
                           10500                                          
                               2.6                                        
8g         2.8 × 10.sup.-3                                          
                 100   22500                                              
                           71600                                          
                               3.1                                        
8h         2.8 × 10.sup.-4                                          
                 40.0  252800                                             
                           421000                                         
                               1.67                                       
8i   -50° C.                                                       
           5.6 × 10.sup.-4                                          
                 58.9  136000                                             
                           334000                                         
                               2.45                                       
8j         1.4 × 10.sup.-3                                          
                 100   38000                                              
                           169000                                         
                               4.5                                        
8k         2.8 × 10.sup.-3                                          
                 100   22900                                              
                           69400                                          
                               3.0                                        
8l         5.6 × 10.sup.-3                                          
                 100   12000                                              
                           35000                                          
                               2.8                                        
8m         2.8 × 10.sup.-2                                          
                 100   1700                                               
                           13000                                          
                               8.0                                        
8n         2.8 × 10.sup.-4                                          
                 32.0  197000                                             
                           340000                                         
                               1.7                                        
8o   -60° C.                                                       
           5.6 × 10.sup.-4                                          
                 17.2  241000                                             
                           383000                                         
                               1.6                                        
8p         1.4 × 10.sup.-3                                          
                 100   35000                                              
                           172900                                         
                               5.0                                        
8q         2.8 × 10.sup.-3                                          
                 100   28000                                              
                           118000                                         
                               4.15                                       
__________________________________________________________________________
EXAMPLE 9
In these runs, the initiator was an unsaturated formate, specifically allyl formate. The polymerization conditions and results of the runs are listed in Table IX.
Thus, in the experimental runs shown in Table IX, the compound of the formula was produced. ##STR20## This new composition of matter has an allyl head group. Molecular weight control was achieved from relatively low molecular weights of less than 8,000 to 10,000 to 13,000 up to very high molecular weights of 40,000 to 50,000 to an excess of 100,000. By use of di-, tri- and higher functional acids or esters, it is possible to produce di-, tri- and higher allyl terminated polyolefins where the polymer may be homo, block or copolymers of the olefins of 2 to about 20 carbon atoms, for example.
              TABLE IX                                                    
______________________________________                                    
Monomer:      isobutylene [M] = 1 mol/l                                   
Initiator:    allylformate [I] = as stated, mol/l                         
Coinitiator:  BCl.sub.3 [BCl.sub.3 ] = 2.6 × 10.sup.-1 mol/l        
Solvent:      CH.sub.3 Cl                                                 
Polymeriza-                                                               
tion Time:    30 minutes                                                  
Temperature:  -30° C.                                              
Run               Conversion                                              
Number [I]        Percent   --M.sub.n                                     
                                  --M.sub.w                               
                                         --M.sub.w --M.sub.n              
______________________________________                                    
9a     5.6 × 10.sup.-4                                              
                  43.4      87000 155000 1.8                              
                  44.8      105000                                        
                                  172100 1.6                              
9b     1.12 × 10.sup.-3                                             
                  77.0      46000 112000 2.4                              
                  74.2      58000 111000 1.9                              
9c     5.6 × 10.sup.-3                                              
                  100       34000 56000  1.6                              
                  100       26000 47000  1.9                              
9d     2.8 × 10.sup.-2                                              
                  100       15600 27100  1.7                              
                  100       13800 23600  1.7                              
9e     5.6 × 10.sup.-2                                              
                  100       10200 19500  1.9                              
                  100       8200  16900  2.1                              
9f     1.12 × 10.sup.-1                                             
                  100       6500  15300  2.3                              
______________________________________
EXAMPLE 10
Another series of runs were made using tert.-butyl acrylate as the initiator, the solvents are listed in Table X. The results of these runs are shown in that table. It should be appreciated that other well known acrylate or methacrylate esters, such as methyl, ethyl or alkyls of 20 or more carbon atoms with the Lewis acids may be used as initiators to produce polymers having ethylenic unsaturation as the end group. Also, the acrylic and methacrylic esters of the diols, triols, tetraols and related polyols of the monomeric to polymeric polyols can be used. Thus, with the polymeric polyols, polymers can be produced having heterogeneous oxygen therein of one or two, up to those of a few hundred to over 5,000 to 10,000.
The following new composition of matter having the important acrylic tail group has been produced: ##STR21## This can be used to crosslink and modify other acrylic or methacrylic polymers. Thus, these reactions with acrylic and methacrylic initiators produce a new generic class of compositions of the following formula: ##STR22## where R is H or CH3. Thus, it is possible by changing the functionality of the acid or ester to produce polymers having one, two, three or more acrylic groups.
                                  TABLE X                                 
__________________________________________________________________________
Monomer:      Isobutylene [M] = 1 mol/l                                   
Initiator:    tert.-butyl acrylate [I] = as stated, mol/l                 
Coinitiator:  BCl.sub.3 [BCl.sub.3 ] = 2.6 × 10.sup.-1 mol/l        
Solvent:      As stated                                                   
Temperature:  -30° C.                                              
Polymeriza-                                                               
tion Time:    30 minutes                                                  
Run                                                                       
Number                                                                    
     Solvent                                                              
          [I]   Conversion %                                              
                        --M.sub.n                                         
                            --M.sub.w                                     
                                --M.sub.w /--M.sub.n                      
__________________________________________________________________________
10a       5.6 × 10.sup.-3                                           
                16.2    --  --  --                                        
10b  CH.sub.3 Cl                                                          
          2.8 × 10.sup.-2                                           
                68.5    3800                                              
                            7200                                          
                                1.9                                       
10c       5.6 × 10.sup.-2                                           
                100     2400                                              
                            4200                                          
                                1.8                                       
10d       5.6 × 10.sup.-3                                           
                76.8    11000                                             
                            42150                                         
                                3.8                                       
10e  CH.sub.2 Cl.sub.2                                                    
          2.8 × 10.sup.-2                                           
                100     4900                                              
                            10700                                         
                                2.2                                       
10f       5.6 × 10.sup.-2                                           
                100     3200                                              
                            6900                                          
                                2.1                                       
__________________________________________________________________________
EXAMPLE 11
To show that lactones, a special class of esters, could act as initiators with the various Lewis acids, a series of runs were made with γ-phenyl-γ-butrolactone as the initiator under conditions shown in Table XI, with the results shown. It should be noted it was possible to make polymers of very low molecular weight, less than about 4,000 to 8,000 and higher molecular weights of greater than 50,000, and the polymer at lower range was liquid to rubbery in the higher range.
                                  TABLE XI                                
__________________________________________________________________________
Monomer: isobutylene [M] = 1 mol/l                                        
Initiator: phenyl- -butyrolactone [I] = as stated, mol/l                  
Coinitiator: BCl.sub.3 [BCl.sub.3 ] = 2.6 × 10.sup.-1 mol/l         
Solvent: CH.sub.3 Cl                                                      
Polymerization Time: 60 minutes unless stated otherwise                   
Temperature: -30° C.                                               
Run         Conversion         Nature of                                  
Number                                                                    
     [I]    Percent                                                       
                  --M.sub.n                                               
                      --M.sub.w                                           
                          --M.sub.w /--M.sub.n                            
                               Product                                    
__________________________________________________________________________
11a  5.6 × 10.sup.-4                                                
            42.6  70300                                                   
                      121700                                              
                          1.8  rubbery                                    
11b         55.7* 51000                                                   
                      91000                                               
                          1.8                                             
11c  1.12 × 10.sup.-3                                               
            22.1  62000                                                   
                      108000                                              
                          1.7  --                                         
11d         53.7* 27000                                                   
                      74000                                               
                          2.7                                             
11e  5.6 × 10.sup.-3                                                
            28.1  17870                                                   
                      33600                                               
                          1.9                                             
11f         5.1*  14500                                                   
                      24400                                               
                          1.7                                             
11g  2.8 × 10.sup.-2                                                
            16.0  6380                                                    
                      33600                                               
                          1.9                                             
11h         54.1* 8500                                                    
                      14300                                               
                          1.7                                             
11i  5.6 × 10.sup.-2                                                
            25.9  4870                                                    
                      8100                                                
                          1.7  liquid                                     
11j         69.8* 6680                                                    
                      10500                                               
                          1.5                                             
11k  1.12 × 10.sup.-1                                               
            100*  4800                                                    
                      7300                                                
                          1.5                                             
__________________________________________________________________________
 *indicates the polymerization time was extended to 2.5 hours.
EXAMPLE 12
In this series of runs at conditions of Table XII, tertiary butyl formate was used to produce polymers of propylene having an oily fluid to a viscous balsam nature. Thus, polypropylene polymers can be produced forming one or more formate terminal groups.
              TABLE XII                                                   
______________________________________                                    
Monomer: Propylene [M] = 1 mol/l                                          
Initiator: Tert-butyl formate [I] = as stated, mol/l                      
Coinitiator: BCl.sub.3 [BCl.sub.3 ] = 2.6 × 10.sup.-1 mol/l         
Solvent: CH.sub.3 Cl                                                      
Temperature: -40° C.                                               
Polymerization Time: 2.5 hours                                            
Run                                                                       
Number [I]         Conversion %                                           
                               Nature of Product                          
______________________________________                                    
12a    5.6 × 10.sup.-4                                              
                   2.2         viscous balsam                             
12b    1.11 × 10.sup.-3                                             
                   6.6         viscous balsam                             
12c    5.6 × 10.sup.-3                                              
                   47.5        viscous fluid                              
12d    5.6 × 10.sup.-2                                              
                   91.9        viscous fluid                              
12e    5.6 × 10.sup.-2                                              
                   97.3        oily fluid                                 
______________________________________
EXAMPLE 13
To prove the living nature of IB or related olefins initated by the supernonnucleophilic counter anion complex, a number of experiments were run and then linear plots of Mn versus grams of polymer formed in the reactor (the figures shown herein) were constructed to see if the plots are linear and whether they cross the origin on extrapolation.
These series of experiments were run in a series of test tubes which were charged with 24 ml CH2 Cl2 2,4,4-trimethylpentyl-2-acetate hereinafter called TMPOAc (5.6×10-3 mol/l) and 0.5 ml IB, in that order, and thermoequilibrated at minus 30° C. Then the polymerization was started by introducing 0.5 ml BCl3 (liquefied) into the test tubes. The BCl3 concentration was 2.8×10-1 mol/l in the reactor. After 30 minutes of reaction time, the reaction in the first of the test tubes was killed by the addition of methanol, whereas an additional 0.5 ml IB was added to the rest of the tubes. After 30 minutes, the reaction in the second tube was killed whereas an additional 0.5 ml IB was added to the remaining tubes. This procedure was repeated until all the charges in the series of test tubes had been quenched. After conventional workup, the amount of polymer and its molecular weight and molecular weight distribution were determined. These data are given in Table XIIIa, and the corresponding plot is given in FIG. 1.
A similar series of experiments have been carried out with a different order of reagent addition. In this experiment, the TMPOAc and BCl3 were premixed in 12 ml CH2 Cl2 and into this system was added 0.5 ml IB dissolved in 12 ml CH2 Cl2 at minus 30° C. Thus, the initial concentrations of the ingredients, i.e., TMPOAc, BCl3 and IB were the same in both series. Except for this premixing of the TMPOAc and BCl3, the further course of the experiment was identical to that described above. FIG. 1 shows the plot of the results.
The fact that the Mn versus grams of PIB formed plot is linear and crosses the origin indicates the living nature of the polymerization system, i.e., each additional monomer increment contributes proportionally to the molecular weight.
The premixing of TMPOAc and BCl3 technique is advantageous as it produces narrower molecular weight distribution polymer than the TMPOAc and monomer and BCl3 addition sequence. This effect can be seen by inspecting the Mw /Mn columns. The Mw /Mn values are lower in the experiment with TMPOAc and BCl3 premixing.
An identical series of experiments have been carried out using CH3 Cl as the diluent. The data is shown in Table XIIIb and these data also yielded a plot similar to that of FIG. 1.
An identical series of experiments have been carried out with the cumyl acetate BCl3 complex initiator in CH2 Cl2 as the solvent. The data are shown in Table XIIIc and are plotted in FIG. 2. Note that one experiment was carried out at a temperature of minus 10° C.
An identical experiment has been carried out with cumyl acetate and BCl3 using CH3 Cl as the diluent. The data are shown in Table XIIId and are plotted in FIG. 3.
Similarly, three identical series of experiments have been carried out with cumyl acetate and BCl3 in various solvent systems. A mixture on a volume basis of 80/20 CH2 Cl2 /n-hexane [Table XIIIe], a mixture of 60/40 CH2 Cl2 [Table XIIIf], and C2 H5 Cl [Table XIIIg]. Corresponding plots of the data from these three experiments, indicated these were living polymerizations.
Finally, a series of experiments have been carried out by the dicumyl acetate BCl3 complex initiator. In this system, polymer growth is expected to occur at both acetae linkages. Table XIIIh and FIG. 4 show the data for these experiments.
              TABLE XIIIa                                                 
______________________________________                                    
Monomer: isobutylene                                                      
Initiator: TMPOAc [I] = 5.6 × 10.sup.-3 mol/l                       
Coinitiator: BCl.sub.3 [BCl.sub.3 ] = 2.8 × 10.sup.-1 mol/l         
Solvent: CH.sub.2 Cl.sub.2 (initial charge: 24 ml)                        
Polymerization Time: 30 minutes between each addition                     
Temperature: -30° C.                                               
Killing with MeOH (˜3 ml, precooled)                                
Run    Isobutylene                    Polymer                             
Number added, ml  --M.sub.n                                               
                          --M.sub.w                                       
                                --M.sub.w /--M.sub.n                      
                                      Formed, g                           
______________________________________                                    
13(a)  0.5        2300    12400 5.5   0.30                                
13(b)  0.5 + 0.5  3900    15700 4.1   0.63                                
13(c)  0.5 + 0.5 +                                                        
                  11600   20050 1.7   1.80                                
       0.5 + 0.5 +                                                        
       0.5 + 0.5                                                          
13(d)  0.5        2900    11350 3.9   0.31                                
13(e)  0.5 + 0.5  4250    15100 3.6   0.59                                
13(f)  0.5 + 0.5 +                                                        
                  8500    18700 2.2   1.20                                
       0.5 + 0.5                                                          
13(g)  0.5 + 0.5 +                                                        
                  11500   18600 1.6   1.80                                
       0.5 + 0.5 +                                                        
       0.5 +  0.5                                                         
13a/h  0.5        3000*   9050  3.0   0.33                                
13a/i  0.5 + 0.5 +                                                        
                  7800    19600 2.5   0.96                                
       0.5                                                                
13a/j  0.5 + 0.5 +                                                        
                  10500   22580 2.1   1.49                                
       0.5 + 0.5 +                                                        
       0.5                                                                
13a/k  0.5 + 0.5 +                                                        
                  13000   22500 1.7   1.76                                
       0.5 + 0.5 +                                                        
       0.5 + 0.05                                                         
______________________________________                                    
 *premixed initiator/coinitiator  helped to narrow MWD.                   

              TABLE XIIIb                                                 
______________________________________                                    
Monomer: isobutylene                                                      
Initiator: TMPOAc [I] = 5.6 × 10.sup.-3 mol/l                       
Coinitiator: BCl.sub.3 [BCl.sub.3 ] = 2.8 × 10.sup.-1 mol/l         
Solvent: CH.sub.3 Cl (initial charge: 24 ml)                              
Polymerization Time: 30 minutes between each addition                     
Temperature: -30° C.                                               
Run    Isobutylene                    Polymer                             
Number added, ml  --M.sub.n                                               
                          --M.sub.w                                       
                                --M.sub.w /--M.sub.n                      
                                      formed, g                           
______________________________________                                    
13b/a  0.5        2700    9950  3.7   0.29                                
13b/b  0.5 + 0.5 +                                                        
                  4420    13800 3.1   0.64                                
       0.5                                                                
13b/c  0.5 + 0.5 +                                                        
       0.5 + 0.5 +                                                        
       0.5 + 0.5  8000    19200 2.4   0.94                                
13b/d  0.5        2800    10900 3.9   0.31                                
13b/e  0.5 + 0.5 +                                                        
       0.5 + 0.5 +                                                        
       0.5 + 0.5  10900   21560 2.0   1.34                                
13b/f  0.5        3000*   7000  2.3   0.33                                
13b/g  0.5 + 0.5  5300    9600  1.8   0.55                                
13b/h  0.5 + 0.5 +                                                        
                  7200    13000 1.8   0.55                                
       0.5                                                                
13b/i  0.5 + 0.5 +                                                        
                  8800    15500 1.76  1.04                                
       0.5 + 0.5                                                          
13b/j  0.5 + 0.5 +                                                        
                  10800   18360 1.7   1.25                                
       0.5 + 0.5 +                                                        
       0.5                                                                
13b/k  0.5 + 0.5 +                                                        
       0.5 + 0.5 +                                                        
       0.5 + 0.5  12850   20560 1.6   1.51                                
______________________________________                                    
 *with premixed initiator/coinitiator (30'); MWD narrowed.                

              TABLE XIIIc                                                 
______________________________________                                    
Monomer: isobutylene                                                      
Initiator: cumyl acetate [I] = 5.6 × 10.sup.-3 mol/l                
Coinitiator: BCl.sub.3 0.5 m BCl.sub.3 added in initial charge            
final [BCl.sub.3 ] = 2.8 × 10.sup.-1 mol/l                          
Solvent: CH.sub.2 Cl.sub.2 (initial charge: 24 ml)                        
Polymerization Time: 30 minutes between each addition                     
Temperature: -30° C.                                               
Run    Isobutylene                    Polymer                             
Number added, ml  --M.sub.n                                               
                          --M.sub.w                                       
                                --M.sub.w /--M.sub.n                      
                                      formed, g                           
______________________________________                                    
13c/a  0.5        3100    6200  2.0   0.31                                
13c/b  0.5 + 0.5  5500    7650  1.4   0.64                                
13c/d  0.5 + 0.5 +                                                        
                  6800    9500  1.4   0.87                                
       0.5                                                                
13c/e  0.5 + 0.5 +                                                        
                  8800    13100 1.48  1.15                                
       0.5 + 0.5                                                          
13c/f  0.5 + 0.5 +                                                        
                  11000   15800 1.4   1.45                                
       0.5 + 0.5 +                                                        
       0.5                                                                
initial solvent charge: 24 ml                                             
13c/g  2          2570    8400  3.2   1.22                                
13c/h  2 + 2      5600    10700 1.9   1.50                                
13c/i  2 + 2 + 2  6900    12400 1.8   3.53                                
13c/j  2 + 2 + 2 +                                                        
                  8900    15800 1.79  4.62                                
       2                                                                  
13c/k  2 + 2 + 2 +                                                        
                  10000   16000 1.6   5.76                                
       2 + 2                                                              
initial solvent charge: 96 ml, 2 ml BCl.sub.3 added, final                
[BCl.sub.3 ] concentration = 2.8 × 10.sup.-1 mol/l                  
______________________________________                                    

              TABLE XIIId                                                 
______________________________________                                    
Monomer: isobutylene                                                      
Initiator: cumyl acetate [I] = 5.6 × 10.sup.-3 mol/l                
Coinitiator: BCl.sub.3 0.5 m BCl.sub.3 added in initial charge            
final [BCl.sub.3 ] = 2.8 × 10.sup.-1 mol/l                          
Solvent: CH.sub.3 Cl (initial charge: 24 ml)                              
Polymerization Time: 30 minutes between each addition                     
Temperature: -30° C.                                               
Killing With: MeOH, ˜3 ml, precooled                                
Run    Isobutylene                    Polymer                             
Number added, ml  --M.sub.n                                               
                          --M.sub.w                                       
                                --M.sub.w /--M.sub.n                      
                                      formed, g                           
______________________________________                                    
13d/a  0.5        2730    5500  2.0   0.31                                
13d/b  0.5 + 0.5  3640    7080  1.94  0.43                                
13d/c  0.5 + 0.5 +                                                        
                  5040    8430  1.67  0.59                                
       0.5                                                                
13d/d  0.5 + 0.5 +                                                        
                  6560    10360 1.58  0.75                                
       0.5 + 0.5                                                          
13d/e  0.5 + 0.5 +                                                        
                  7160    11620 1.6   0.90                                
       0.5 + 0.5 +                                                        
       0.5                                                                
13d/f  0.5 + 0.5 +                                                        
       0.5 + 0.5 +                                                        
       0.5 + 0.5  8440    12850 1.5   1.12                                
13d/g  0.25       1500    3040  2.0   0.14                                
13d/h  0.25 + 0.25                                                        
                  1860    3200  1.7   0.20                                
13d/i  0.25 + 0.25 +                                                      
                  2530    4850  1.9   0.32                                
       0.5                                                                
13d/j  0.25 + 0.25 +                                                      
                  3800    7830  2.0   0.50                                
       0.5 + 0.5                                                          
13d/k  0.25 + 0.25 +                                                      
       0.5 + 0.5 +                                                        
       0.5        4900    9500  1.9   0.60                                
13d/l  0.25 + 0.25 +                                                      
       0.5 + 0.5 +                                                        
       0.5 + 0.5  6600    12000 1.7   0.76                                
______________________________________                                    
 The plot of this data is shown in FIG. 4.                                

              TABLE XIIIe                                                 
______________________________________                                    
Monomer: isobutylene                                                      
Initiator: cumyl acetate [I] = 5.6 × 10.sup.-3 mol/l                
Coinitiator: BCl.sub.3 [BCl.sub.3 ] 2.8 × 10.sup.-1 mol/l           
Solvent: CH.sub.2 Cl.sub.2 /n-hexane, 80 v/20 v (initial charge 24 ml)    
Polymerization Time: 30 minutes between each addition                     
Temperature: -30° C.                                               
Run    Isobutylene                     Polymer                            
Number added, ml   --M.sub.n                                              
                          --M.sub.w                                       
                                 --M.sub.w /--M.sub.n                     
                                       formed, g                          
______________________________________                                    
13e/a  0.5         3500   5560   1.59  0.36                               
13e/b  0.5 + 0.5 + 4880   12950  2.66  0.55                               
       0.5                                                                
13e/c  0.5 + 0.5 + 5400   16100  3.0   0.66                               
       0.5 + 0.5                                                          
______________________________________                                    

              TABLE XIIIf                                                 
______________________________________                                    
Monomer: isobutylene                                                      
Initiator: cumyl acetate [I] = 5.6 × 10.sup.-3 mol/l                
Coinitiator: BCl.sub.3 [BCl.sub.3 ] 2.8 × 10.sup.-1 mol/l           
Solvent: CH.sub.2 Cl.sub.2 /n-hexane, 60 v/40 v (initial charge 24 ml)    
Polymerization Time: 30 minutes between each addition                     
Temperature: -30° C.                                               
Run    Isobytylene                     Polymer                            
Number added, ml   --M.sub.n                                              
                          --M.sub.w                                       
                                 --M.sub.w /--M.sub.n                     
                                       formed, g                          
______________________________________                                    
13f/a  0.5         3450   6500   1.88  0.35                               
13f/b  0.5 + 0.5 + 4580   11390  2.48  0.43                               
       0.5 + 0.5 +                                                        
       0.5                                                                
13f/c  0.5 + 0.5 + 4750   12000  2.5   0.47                               
       0.5 + 0.5 +                                                        
       0.5 + 0.5                                                          
______________________________________                                    

              TABLE XIIIg                                                 
______________________________________                                    
Monomer: isobutylene                                                      
Initiator: cumyl acetate [I] = 5.6 × 10.sup.-3 mol/l                
Coinitiator: BCl.sub.3 [BCl.sub.3 ] 2.8 × 10.sup.-1 mol/l           
Solvent: C.sub.2 H.sub.5 Cl (initial charge 24 ml)                        
Polymerization Time: 30 minutes between each addition                     
Temperature: -30° C.                                               
Run    Isobutylene                     Polymer                            
Number added, ml   --M.sub.n                                              
                           --M.sub.w                                      
                                 --M.sub.w /--M.sub.n                     
                                       formed, g                          
______________________________________                                    
13g/a  0.5         3150    4830  1.5   0.33                               
13g/b  0.5 + 0.5   3400    6400  1.9   0.40                               
13g/c  0.5 + 0.5 + 3900    9720  2.49  0.47                               
       0.5                                                                
13g/d  0.5 + 0.5 + 4100    11520 2.8   0.54                               
       0.5 + 0.5                                                          
13g/e  0.5 + 0.5 + 5100    11350 2.8   0.61                               
       0.5 + 0.5 +                                                        
       0.5                                                                
12g/f  0.5 + 0.5 +                                                        
       0.5 + 0.5 +                                                        
       0.5 + 0.5   5200    16370 3.1   0.66                               
______________________________________                                    

              TABLE XIIIh                                                 
______________________________________                                    
Monomer: isobutylene                                                      
Initiator: dicumyl acetate [I] = 5.6 × 10.sup.-3 mol/l              
Coinitiator: BCl.sub.3 [BCl.sub.3 ] 2.8 × 10.sup.-1 mol/l           
Solvent: CH.sub.3 Cl (initial charge 24 ml)                               
Polymerization Time: 30 minutes between each addition                     
Temperature: -30° C.                                               
Run    Isobutylene                     Polymer                            
Number added, ml   --M.sub.n                                              
                           --M.sub.w                                      
                                 --M.sub.w /--M.sub.n                     
                                       formed, g                          
______________________________________                                    
13h/a  0.5         1730    3090  1.78  0.32                               
13h/b  0.5 + 0.5   2790    4750  1.7   0.54                               
13h/c  0.5 + 0.5 + 4260    6560  1.54  0.85                               
       0.5                                                                
13h/d  0.5 + 0.5 + 5300    7610  1.44  1.09                               
       0.5 + 0.5                                                          
13h/e  0.5 + 0.5 + 6500    9430  1.45  1.28                               
       0.5 + 0.5 +                                                        
       0.5                                                                
13h/f  0.5 + 0.5 + 7000    9760  1.39  1.47                               
       0.5 + 0.5 +                                                        
       0.5 + 0.5                                                          
______________________________________
A special embodiment of this invention relates to the random copolymerization of an alphaolefin such as those exemplified by isobutylene, propylene, pentene or hexene, with a diolefin, preferably a conjugated one such as those exemplified by isoprene, butadiene and piperylene. Thus, copolymers containing either a major or minor amount of diolefin can be produced. Isobutylene plus an isoprene copolymer containing up to 5 percent isoprene in the chain are articles of commerce. The random polymers produced by this invention have commercial utility as butyl rubbers and especially those having a molecular weight of a hundred thousand and 1 to 4 percent unsaturation. These rubbers are sulfurvulcanizable, heat stable, chemically resistant general purpose rubbers which may be used in inner tubes and inner liners of tires, tubes, curing bladders, mountings, vibration dampers, etc., and are convertible to the halogenated form of butyl rubber for other usages. Heretofore, butyl rubber was made commercially by a heterogeneous low temperature (minus 100° C.) cationic suspension polymerization by the use of AlCl3 catalyst in methyl chloride diluent. In order to obtain commercially useful molecular weights, the polymerization has to be carried out at cryogenic tempertures, viz. below minus 100° C. Therefore, a lot of work has been directed towards the raising of this very low temperature requirement. Also, controlling molecular weight with the AlCl3 system is difficult, it requires changes in reactor temperature. Another problem with conventional polymerizations is reactor fauling. Fauling is the process during which polymer particles crosslink and agglomerate during the run and precipitate on the inner surfaces of the reactor. This adhering layer of crosslinked or gelled polymer decreases cooling efficiency so that molecular weight control becomes impossible. Thus, the reactor has to be shut off and the fauled polymer layer removed by a separate cumbersome and costly process. Great efforts have been extended to overcome fauling.
In Example 14, copolymerization of isobutylene with isoprene was demonstrated to occur readily with our complex catalyst, and that the copolymerization yields random copolymers whose overall composition can be controlled by the isobutylene/isoprene ratio in that charge, and that the molecular weight of the butyl rubber formed can be controlled by the ratio of [monomers]/[initiating complex], and that the copolymerization is living in nature. Also, the percent unsaturation can be controlled over a wide molecular weight range to yield new copolymers of alpha-olefins and dienes which may have higher molecular weights, i.e., in excess of a hundred thousand molecular weight and having unsaturation values of 1, 2, 3 to 5 mole percent and higher. Thus, copolymers having 1 to 90 and preferably 2 to 10 percent of diolefin are readily made.
EXAMPLE 14
A series of copolymerization experiments have been carried out under the following conditions: A series of three test tubes have been charged at minus 30° C. with 22.5 ml CH3 Cl, 2.0 ml isobutylene (0.94 mole/l) and 0.1 ml cumyl acetate (0.56×10-3 mole/l) in that order. Then in a series of three test tubes, isoprene was introduced, i.e., 0.05 ml (or 2.13 mole percent on isobutylene); 0.1 ml (or 4.26 mole percent on isobutylene); and 0.2 ml (or 8.52 mole percent on isobutylene) isoprene. Finally, the copolymerizations were initiated by the introduction of 0.5 ml BCl3 (2.8 10-1 mole/l). The polymerizations proceeded with occasional mixings at minus 30° C. for 30 minutes. Then the reactions were killed by adding 3 ml of prechilled methanol. After workup, the conversions, molecular weights, and overall compositions were determined. The latter was obtained by 1 H NMR spectroscopy which also indicated that the product contained the isoprene units in the chain in a 1,4-enchainment. Table XIV shows this data.
              TABLE XIV                                                   
______________________________________                                    
Monomer: isobutylene [M.sub.1 ] = 0.94 mol/l                              
isoprene [M.sub.2 ] = as stated, mol/l                                    
Initiator: cumyl acetate [I] = 5.6 × 10.sup.-3 mol/l                
Coinitiator: BCl.sub.3 [BCl.sub.3 ] 2.8 × 10.sup.-1 mol/l           
Solvent: CH.sub.3 Cl (initial charge 22.5 ml)                             
Polymerization Time: 30 minutes                                           
Temperature: -30° C.                                               
                                          Isoprene                        
                 Con-                     in the                          
Run              ver-                     polymer,                        
Number [M.sub.2 ]                                                         
                 sion %  --M.sub.n                                        
                              --M.sub.w                                   
                                    --M.sub.n /.sub.--M.sub.w             
                                          mole %                          
______________________________________                                    
14a    0.02      85.0    9100 13100 1.48  --                              
       (2.13 m %)                                                         
14b    0.04      74.3    7150 11400 1.6   2.91                            
       (4.26 m %)                                                         
14c    0.08      51.8    5300 9300  1.75  4.3                             
       (8.52 m %)                                                         
______________________________________
EXAMPLE 15
Two additional series were carried out to demonstrate the living nature of the copolymerization. The charging of the series of tubes and the polymerization conditions have been described above in Example 14. In the first series of copolymerizations, three tubes were charged to give 4.26 mole percent isoprene in the isoprene solution (relative to isobutylene). After BCl3 addition, the reactions in the first, second and third tubes were killed at 25, 30 and 45 minutes. After workup, the conversions and molecular weights were determined. The data is shown in Table XVa and FIG. 5.
The second series of copolymerizations have been carried out with 2.13 mole percent isoprene (on isobutylene) in the charge. Copolymerizations were terminated after 5 and 10 minutes after BCl3 addition. In the third tube at 20 minutes, we added a fresh charge of 2.05 ml monomer mixture consisting of 2.0 ml isobutylene and 0.05 ml isoprene, i.e., a charge of 2.13 mole percent isoprene (on isobutylene), and allowed the reaction to proceed for an additional 30 minutes. After killing and workup, the conversion and the molecular weight of the polymers were determined. Table XVb and FIG. 5 show the results.
According to these data, the copolymerizations proceeded in a living manner as indicated by the linear Mn versus conversion plots crossing the origin.
The polymerizations described in this invention can be carried out as long as the initiating complex maintains its integrity to give a wide range of molecular weights. Tests determined that the tert.-butyl acetate BCl3 complex is stable up until at least minus 10° C. Therefore, living and other polymerization can be carried out up to at least minus 10° C. and even to the decomposition temperature of the complex which in most cases is near ambient or 10°-30° C. below it, but some initiator complexes allows operating tempertures above 0° C. Thus, butyl rubber can be made at much higher temperatures than heretofore.
              TABLE XVa                                                   
______________________________________                                    
Monomer: isobutylene [M.sub.1 ] = 0.94 mol/l                              
isoprene [M.sub.2 ] = 0.04 mol/l (4.26 mol %)                             
Initiator: cumyl acetate [I] = 5.6 × 10.sup.-3 mol/l                
Coinitiator: BCl.sub.3 [BCl.sub.3 ] 2.8 × 10.sup.-1 mol/l           
Solvent: CH.sub.3 Cl (initial charge 22.5 ml)                             
Polymerization Time: as stated                                            
Temperature: -30° C.                                               
Run    Polymerization                                                     
                   Conversion                                             
Number Time        %         --M.sub.n                                    
                                   --M.sub.w                              
                                         --M.sub.w /--M.sub.n             
______________________________________                                    
15a/a  15 minutes  58.0      5800  10480 1.8                              
15a/b  30 minutes  74.9      6900  11700 1.69                             
15a/c  45 minutes  79.3      7500  11600 1.55                             
______________________________________                                    

              TABLE XVb                                                   
______________________________________                                    
Monomer: isobutylene [ M.sub.1 ] = 0.94 mol/l                             
isoprene [M.sub.2 ] = 0.02 mol/l (2.13 mol %)                             
Initiator: cumyl acetate [I] = 5.6 × 10.sup.-3 mol/l                
Coinitiator: BCl.sub.3 [BCl.sub.3 ] 2.8 × 10.sup.-1 mol/l           
Solvent: CH.sub.3 Cl (initial charge 22.5 ml)                             
Polymerization Time: as stated                                            
Temperature: -30° C.                                               
Run    Polymerization                                                     
                   Conversion                                             
Number Time        %         --M.sub.n                                    
                                   --M.sub.w                              
                                         --M.sub.w /--M.sub.n             
______________________________________                                    
15b/a  5 minutes   77.1      7120  11400 1.6                              
15b/b  10 minutes  84.7      8450  13400 1.55                             
15b/c  25 minutes  --        --    --    --                               
15b/d  30 minutes* 100 + 18.5                                             
                             11200 16050 1.44                             
______________________________________                                    
 *After 20 minutes polymerization time, 2.05 ml new isobutylene (2 ml)    
 isoprene (0.05 ml = 2.13 m %) mixture was added and was allowed to       
 polymerize for 30 minutes.
EXAMPLE 16
In this example, 0.06 ml tert.-butyl acetate (t-BuAC) and 0.2 ml BCl3 were mixed in 20 ml CH2 Cl2 at minus 10° C. After 1 hour at this temperature, the IR spectrum of the system (taken against the CH2 Cl2 solvent by the use of the matched cells) indicated the presence of the t-BuAC.BCl3 complex; i.e., presence of an absorption at 1570 cm-1 associated with the stretching vibration of the >C═O→BCl3 group (the uncomplexed >C═O shows νCO=1720 cm-1 in t-BuOAC).
Upon heating the t-BuAC.BCl3 complex to room temperature, the complex slowly decomposes to t-BuCl and CH3 COCl (νCO=1800 cm-1 in CH3 COCl). After one hour at room temperature, 50 percent of the complex has decomposed.
Similar to these experiments, the TMPOAc.BCl3 complex is stable up until minus 10° C. but it decomposes quantitatively at room temperature to TMP-Cl and CH3 COCl, upon standing at this temperature for sufficient time.
The above two experiments can be regarded as model experiments for these polymer systems. Thus when a polymer prepared by the t-BuAC.BCl3 system in which CH3 Cl diluent at minus 30° C. after 30 minutes polymerization was examined, it showed the characteristic CO=1570 cm-1 vibration, indicating the presence of >CO BCl3 complex bond. After letting the system warm to room temperature overnight without killing the reaction, both 1 H NMR and IR spectroscopy showed the formation of an allyl chloride and CH3 COCl.
The fact that the polymer readily decomposes to the tert.-chloride ended structure has important preparative/synthetic implications as it provides a new avenue to valuable tert-chlorine terminated polymers. It is immediately apparent that by the use of difunctional acetate.BCl3 complex initiators, i.e., dicumyl acetate.BCl3 or other diacetates.BCl3 complexes, valuable telechelic polyisobutylenes and related alpha-oelfins or diolefin polymers can be prepared.
We have also discovered that the tert.-chloride groups can be quantitatively obtained not only by treating the polymerizing system to bring it to room temperature, but also by adding various nucleophilic killing or quenching agents, i.e., CH3 OH, (C2 H5)3 N, pyridine, ammonia, methanol, and sodium methoxide. These experiments were carried out by model and subsequent polymerization studies to show that any of the olefins can be polymerized by the Lewis acid organic acid or ester complex to give a novel polymerization process to produce new polymers.
New compositions of matter having the structure set forth in the formulae below can be made by this invention. ##STR23## where R1 is hydrogen, halogen or an organic moiety of an organic acid;
R2 is the same as R1 ;
R3 is the same as R2 ;
R4 is methylene or polymethylene, ethylenic, acetylenic, ##STR24## or related homologous groups; R8 is a trivalent organic moiety; and
y is hydrogen or alkyl.
While in accordance with the patent statutes only the best mode and preferred embodiment of the invention has been illustrated and described in detail, it is to be understood that the invention is not limited thereto or thereby, but that the scope of the invention is defined by the appended claims.

Claims (16)

What is claimed is:
1. A method of producing a complex of an organic carboxylic acid or ester with a Lewis acid that forms supernonnucleophilic counter anion and characterized by its ability to add olefin monomers to give a living polymerization system comprising introducing an organic carboxylic acid or ester and a Lewis acid into a system and mixing without regard to sequence at a temperature below the decomposition-temperature of said complex in the presence or absence of a solvent for said complex; said system containing sufficient olefin relative to [M]o/[I]o ratio to give the complex a molecular weight greater than 1000, where [M]o and [I]o are the initial momomer and initiator concentration, respectively.
2. The method of claim 1 wherein the temperature is below minus 10° C.
3. The method of claim 1 wherein the Lewis acid is selected from the class consisting of BCl3, AlCl3, TiCl4, SbF5, FeCl3, ZnCl2 and VCl4.
4. The method of claim 1 wherein the Lewis acid is boron chloride.
5. The method of claim 1 wherein sufficient olefin monomer has been added while maintaining the temperature below the decomposition temperature of said complex to increase its molecular weight to within a range of greater than 1,000 to above a hundred thousand.
6. The method of claim 1 wherein the olefin reacts with the complex to give a polymer complex and to consume essentially all said olefin within a few minutes but still has ability to add more olefin.
7. The method of claim 1 wherein the molecular weight increase of said complex is proportional to monomer concentration divided by concentration of initiator concentration.
8. The method of claim 1 wherein sufficient olefin monomers is contacted with said complex to increase its molecular weight to at least 1,000.
9. The method of claim 1 wherein the complex and olefin are fed simultaneously to a reactor and the temperature produced by mixing said complex and olefin would require less than 10 minutes to decompose half of the said complex fed to the reactor.
10. A method of producing a complex of an organic carboxylic acid or ester with a Lewis acid and increasing the molecular weight of said complex by adding olefinic monomers thereto to effect a carbocationic polymerization comprising:
forming a complex of said organic carboxylic acid or ester with a Lewis acid by contacting said organic carboxylic acid or ester with said Lewis acid at a temperature below the temperature at which said complex decomposes, contacting said complex prior to substantial decomposition with at least one olefin to effect a significant increase in molecular weight of said complex to greater than 1,000.
11. The method of claim 10 wherein the temperature of the complex is below 0° C. and the olefin has a temperature sufficient to produce a mixture having a temperature above decomposition temperature of the complex upon mixing and maintaining said mixture at said temperature above the decomposition temperature of said complex but sufficiently high that less than half of the complex is decomposed in half an hour.
12. The method of claim 10 wherein the complex and olefin are fed simultaneously to a reactor and the temperature of mixture produced by their intimate mixing is above the decomposition temperature of the complex.
13. The method of claim 1 wherein the mixture temperature is about 10° to less than 50° C.
14. The method of claim 1 wherein the polymerization rate is sufficient to essentially consume all the olefin in a few minutes and the complex has a decomposition half life greater than time required to consume all the olefin.
15. The method of claim 1 wherein the complex has a decomposition half life of at least 10 minutes at a temperature of 10° C.
16. The method of claim 10 wherein polymerization occurs at a temperature above the decomposition temperature of the complex and the rate of decomposition of the complex at this temperature does not effect [M]/[I] ratio sufficient to cause the Mw /Mn ratio to vary more than about 1.0 to 3.5.
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Cited By (86)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5260383A (en) * 1991-04-17 1993-11-09 Polysar Rubber Corporation Polyisobutylene based block copolymers
US5350819A (en) * 1993-02-19 1994-09-27 Exxon Chemical Patents Inc. Carbocationic catalysts and process for using said catalysts
US5376744A (en) * 1993-11-10 1994-12-27 The University Of Akron Carbocationic polymerizations in supercritical CO2
US5448000A (en) * 1994-02-17 1995-09-05 New Mexico Tech Research Foundation End-quenching the living polymerization of isobutylene with acetyl sulfate
US5506316A (en) * 1993-02-19 1996-04-09 Exxon Chemical Patents Inc. Carbocationic catalysts and process for using said catalysts
US5523359A (en) * 1995-01-13 1996-06-04 Exxon Chemical Patents Inc. Functionalized polymer and methods to obtain functionalized polymer
US5665837A (en) * 1993-12-23 1997-09-09 University Of Massachusetts Lowell Initiation via haloboration in living cationic polymerization
US5708103A (en) * 1995-02-01 1998-01-13 Kuraray Co., Ltd. Process for producing a polymer of vinylic compounds
US5721331A (en) * 1995-03-08 1998-02-24 Kuraray Co., Ltd. Isobutylene-based polymer and process of producing the same
WO1998013391A1 (en) * 1996-09-26 1998-04-02 Arizona Chemical Company Process for cationic polymerization
US5741331A (en) * 1996-07-29 1998-04-21 Corvita Corporation Biostable elastomeric polymers having quaternary carbons
US6130291A (en) * 1998-06-04 2000-10-10 The University Of Akron Dynamic star polymers and a method for the synthesis thereof
US6265486B1 (en) 1998-12-31 2001-07-24 Exxon Mobil Chemical Patents Inc. Triblock copolymers incorporating a styrene/isoolefin copolymer midblock
US6274689B1 (en) 1998-10-07 2001-08-14 Exxon Chemical Patents, Inc. Random isomonoolefin/allyl styrene copolymers and functionalized derivatives thereof
US6291389B1 (en) 1994-04-28 2001-09-18 Exxonmobil Chemical Patents Inc. Cationic polymerization catalysts
US6545097B2 (en) 2000-12-12 2003-04-08 Scimed Life Systems, Inc. Drug delivery compositions and medical devices containing block copolymer
US20040018312A1 (en) * 2002-07-25 2004-01-29 Lord Corporation Ambient cured coatings and coated rubber products therefrom
US20040063879A1 (en) * 2001-01-24 2004-04-01 Baird Michael C. Process for making high molecular weight isobutylene polymers
US20040068036A1 (en) * 2002-10-07 2004-04-08 Halladay James R. Flexible emissive coatings for elastomer substrates
US20040260033A1 (en) * 2003-06-19 2004-12-23 Stokes Casey D. Living and quasiliving cationic telechelic polymers quenched by N-substituted pyrrole and methods for their preparation
US20050125003A1 (en) * 2003-12-05 2005-06-09 Leonard Pinchuk Glaucoma implant device
US20050125059A1 (en) * 2003-12-05 2005-06-09 Leonard Pinchuk Ocular lens
US20050143526A1 (en) * 2003-06-20 2005-06-30 Rudolf Faust End-capped polymer chains and products thereof
US20050165182A1 (en) * 2002-01-21 2005-07-28 Manfred Bochmann Process for preparing isobutylene-based polymers
US20050176891A1 (en) * 2004-02-11 2005-08-11 Rudolf Faust Copolymers comprising olefin and protected or unprotected hydroxystyrene units
US20050176903A1 (en) * 2004-02-11 2005-08-11 Rudolf Faust End-capped polymer chains and products thereof
US20050187414A1 (en) * 2003-07-31 2005-08-25 Rudolf Faust Copolymers comprising branched olefin and vinyl ether units
EP1491573A4 (en) * 2002-03-29 2005-09-21 Takashi Sawaguchi Novel polyesterified block copolymer and process for producing the same
US20060041084A1 (en) * 2004-08-20 2006-02-23 Chevron Oronite Company Llc Method for preparation of polyolefins containing exo-olefin chain ends
US20060041083A1 (en) * 2004-08-20 2006-02-23 Chevron Oronite Company Llc Method for preparation of polyolefins containing exo-olefin chain ends
US20060041081A1 (en) * 2004-08-20 2006-02-23 Chevron Oronite Company Llc Method for preparing polyolefins containing a high percentage of exo-olefin chain ends
US20060045900A1 (en) * 2004-08-27 2006-03-02 Robert Richard Embolization
US20060127198A1 (en) * 2002-09-11 2006-06-15 Bsh Bosch Und Siemens Hausgerate Gmbh Liquor container for a washing machine
US20070093604A1 (en) * 2003-07-01 2007-04-26 Joseph Kennedy Thermoplastic elastomeric multiblock copolymers of isobutylene and norbornene
US20070118066A1 (en) * 2004-12-03 2007-05-24 Leonard Pinchuk Glaucoma Implant Device
US20070123812A1 (en) * 2004-12-03 2007-05-31 Leonard Pinchuk Glaucoma Implant Device
US20070141340A1 (en) * 2005-12-21 2007-06-21 Young-Ho Song Block copolymer particles
US20070141339A1 (en) * 2005-12-21 2007-06-21 Young-Ho Song Block copolymer particles
US20070142560A1 (en) * 2005-12-21 2007-06-21 Young-Ho Song Block copolymer particles
US20070141116A1 (en) * 2004-12-03 2007-06-21 Leonard Pinchuk Glaucoma Implant Device
US20070155910A1 (en) * 2005-12-30 2007-07-05 Chevron Oronite Company Llc Method for preparing polyolefins containing vinylidine end groups using polymeric nitrogen compounds
US20070155908A1 (en) * 2005-12-30 2007-07-05 Stokes Casey D Method for preparing polyolefins containing vinylidine end groups using azole compounds
US20070155911A1 (en) * 2005-12-30 2007-07-05 Stokes Casey D Method for preparing polyolefins containing vinylidine end groups using nonaromatic heterocyclic compounds
EP1932859A2 (en) 2006-12-15 2008-06-18 Chevron Oronite Company LLC Polyisobutenyl sulfonates having low polydispersity
US20090068271A1 (en) * 2007-09-12 2009-03-12 Boston Scientific Scimed, Inc. Embolization particles
US7553546B1 (en) 2005-11-16 2009-06-30 Pacesetter, Inc. Polyethylene oxide and silicone copolymers and their usage on medical devices
US20090247716A1 (en) * 2008-03-25 2009-10-01 Stokes Casey D Production of Vinylidene-Terminated Polyolefins Via Quenching with Monosulfides
US20090318624A1 (en) * 2008-06-24 2009-12-24 Storey Robson F Preparation of exo-olefin terminated polyolefins via quenching with alkoxysilanes or ethers
US20100099835A1 (en) * 2008-10-22 2010-04-22 Stokes Casey D Production of Vinylidene-Terminated and Sulfide-Terminated Telechelic Polyolefins Via Quenching with Disulfides
US7708774B1 (en) 2005-11-16 2010-05-04 Pacesetter, Inc. Polyethylene oxide and silicone copolymers and their usage on medical devices
US7715922B1 (en) 2005-11-16 2010-05-11 Pacesetter, Inc. Polyethylene oxide and polyisobutylene copolymers and their usage on medical devices
US20100168339A1 (en) * 2004-02-11 2010-07-01 Rudolf Faust Novel methods for forming copolymers comprising olefin and protected or unprotected hydroxystyrene units
US20100249001A1 (en) * 2009-03-31 2010-09-30 Storey Robson F Amine-terminated telechelic polymers and precursors thereto and methods for their preparation
US20110028681A1 (en) * 2009-07-31 2011-02-03 Storey Robson F In situ formation of hydroxy chain end functional polyolefins
US20110054580A1 (en) * 2009-09-02 2011-03-03 Shrojalkumar Desai Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same
US20110060082A1 (en) * 2009-09-08 2011-03-10 Mutsuki Sugimoto Polymer composition and pneumatic tire
US20110056612A1 (en) * 2009-09-10 2011-03-10 Mutsuki Sugimoto Method for Producing Polymer Sheet for Inner Liner and Method for Producing Pneumatic Tire
US20110068508A1 (en) * 2009-09-18 2011-03-24 Mutsuki Sugimoto Method for producing pneumatic tire
US20110077357A1 (en) * 2009-09-30 2011-03-31 Mutsuki Sugimoto Polymer composition for inner liner and pneumatic tire using the same
WO2011075536A2 (en) 2009-12-18 2011-06-23 Chevron Oronite Company Llc Carbonyl-ene functionalized polyolefins
US20110166425A1 (en) * 2008-09-05 2011-07-07 Edelman David S Flexible Disposable Surgical Port
US8344073B2 (en) 2009-01-16 2013-01-01 The University Of Southern Mississippi Functionalization of polyolefins with phenoxy derivatives
CN101955558B (en) * 2009-07-15 2013-03-13 北京化工大学 Initiating system for preparing high-reaction activity polyisobutene and copolymer of polyisobutene
US8492491B2 (en) 2010-06-10 2013-07-23 Chevron Oronite Company Llc Methods for producing telechelic polyolefins from terpene initiators
US8501831B2 (en) 2008-06-27 2013-08-06 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical devices containing the same
WO2013147978A2 (en) 2012-01-12 2013-10-03 Innfocus, Inc. Method, surgical kit and device for treating glaucoma
US8592527B2 (en) 2010-06-14 2013-11-26 University Of Southern Mississippi Vinyl ether end-functionalized polyolefins
US8656973B2 (en) 2010-07-30 2014-02-25 Sumitomo Rubber Industries, Ltd. Polymer sheet for inner liner, polymer laminate for inner liner, and pneumatic tire
US8660663B2 (en) 2010-12-20 2014-02-25 Cardiac Pacemakers, Inc. Lead having a conductive polymer conductor
EP2712809A1 (en) 2007-10-19 2014-04-02 Lord Corporation Suspension system for aircraft auxilliary power unit with elastomeric member
US20140107310A1 (en) * 2012-10-12 2014-04-17 Basf Se Process for preparing polyisobutenes
US8815033B2 (en) 2010-06-29 2014-08-26 Sumitomo Rubber Industries, Ltd. Method for producing pneumatic tire and pneumatic tire
US8893756B2 (en) 2010-07-07 2014-11-25 Sumitomo Rubber Industries, Ltd. Polymer sheet for inner liner and pneumatic tire using the same
US8927660B2 (en) 2009-08-21 2015-01-06 Cardiac Pacemakers Inc. Crosslinkable polyisobutylene-based polymers and medical devices containing the same
US8942823B2 (en) 2009-09-02 2015-01-27 Cardiac Pacemakers, Inc. Medical devices including polyisobutylene based polymers and derivatives thereof
US8962785B2 (en) 2009-01-12 2015-02-24 University Of Massachusetts Lowell Polyisobutylene-based polyurethanes
US8969484B2 (en) 2011-07-08 2015-03-03 Chevron Oronite Company Llc Methods of producing mono- and multi-functional polymers from terpene-based initiators
US9676234B2 (en) 2010-12-06 2017-06-13 Sumitomo Rubber Industries, Ltd. Strip, method for manufacturing the same, and method for manufacturing pneumatic tire
US9855798B2 (en) 2011-07-28 2018-01-02 Sumitomo Rubber Industries, Ltd. Pneumatic tire
US9926399B2 (en) 2012-11-21 2018-03-27 University Of Massachusetts High strength polyisobutylene polyurethanes
US10046532B2 (en) 2010-11-17 2018-08-14 Sumitomo Rubber Industries, Ltd. Method for manufacturing pneumatic tire
US10239271B2 (en) 2010-11-05 2019-03-26 Sumitomo Rubber Industries, Ltd. Strip, method for manufacturing the same, and method for manufacturing pneumatic tire
US10272721B2 (en) 2012-08-01 2019-04-30 Sumitomo Rubber Industries, Ltd. Pneumatic tire including inner liner
US10526429B2 (en) 2017-03-07 2020-01-07 Cardiac Pacemakers, Inc. Hydroboration/oxidation of allyl-terminated polyisobutylene
US10835638B2 (en) 2017-08-17 2020-11-17 Cardiac Pacemakers, Inc. Photocrosslinked polymers for enhanced durability
US11472911B2 (en) 2018-01-17 2022-10-18 Cardiac Pacemakers, Inc. End-capped polyisobutylene polyurethane

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2415172A (en) * 1944-07-25 1947-02-04 Standard Oil Dev Co Production of polymers from alcohols using a boron fluoride-acetic acid complex catalyst
US2588358A (en) * 1948-04-22 1952-03-11 Standard Oil Dev Co Process for polymerization of propylene with liquid catalyst complex
GB734498A (en) * 1951-12-31 1955-08-03 Exxon Research Engineering Co Polymerisation of olefins
US3210408A (en) * 1961-04-05 1965-10-05 Haarmann & Reimer Gmbh Processes for the production of unsaturated esters
US3862101A (en) * 1971-02-22 1975-01-21 Cpc International Inc Acrylate and methacrylate terminated polydiene macromolecular monomers having a substantially uniform molecular weight distribution
US3963772A (en) * 1973-02-09 1976-06-15 E. I. Du Pont De Nemours And Company Alternating alkylene/acrylic telomers
US4031159A (en) * 1975-07-29 1977-06-21 Lion Fat & Oil Co., Ltd. Method for preparation of polyolefin oil

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2415172A (en) * 1944-07-25 1947-02-04 Standard Oil Dev Co Production of polymers from alcohols using a boron fluoride-acetic acid complex catalyst
US2588358A (en) * 1948-04-22 1952-03-11 Standard Oil Dev Co Process for polymerization of propylene with liquid catalyst complex
GB734498A (en) * 1951-12-31 1955-08-03 Exxon Research Engineering Co Polymerisation of olefins
US3210408A (en) * 1961-04-05 1965-10-05 Haarmann & Reimer Gmbh Processes for the production of unsaturated esters
US3862101A (en) * 1971-02-22 1975-01-21 Cpc International Inc Acrylate and methacrylate terminated polydiene macromolecular monomers having a substantially uniform molecular weight distribution
US3963772A (en) * 1973-02-09 1976-06-15 E. I. Du Pont De Nemours And Company Alternating alkylene/acrylic telomers
US4031159A (en) * 1975-07-29 1977-06-21 Lion Fat & Oil Co., Ltd. Method for preparation of polyolefin oil

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Kennedy et al., J. Polymer Science, Polymer Chem. Ed., vol. 18, 1523 1537, 1539 1540 (1980). *
Kennedy et al., J. Polymer Science, Polymer Chem. Ed., vol. 18, 1523-1537, 1539-1540 (1980).

Cited By (162)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5260383A (en) * 1991-04-17 1993-11-09 Polysar Rubber Corporation Polyisobutylene based block copolymers
US5362817A (en) * 1991-04-17 1994-11-08 Polysar Rubber Corporation Polyisobutylene based block copolymers
US5350819A (en) * 1993-02-19 1994-09-27 Exxon Chemical Patents Inc. Carbocationic catalysts and process for using said catalysts
US5506316A (en) * 1993-02-19 1996-04-09 Exxon Chemical Patents Inc. Carbocationic catalysts and process for using said catalysts
US5376744A (en) * 1993-11-10 1994-12-27 The University Of Akron Carbocationic polymerizations in supercritical CO2
US5665837A (en) * 1993-12-23 1997-09-09 University Of Massachusetts Lowell Initiation via haloboration in living cationic polymerization
US5448000A (en) * 1994-02-17 1995-09-05 New Mexico Tech Research Foundation End-quenching the living polymerization of isobutylene with acetyl sulfate
US6699938B2 (en) 1994-04-28 2004-03-02 Exxonmobil Chemical Patents Inc. Cationic catalysts and process for using said catalysts
US6291389B1 (en) 1994-04-28 2001-09-18 Exxonmobil Chemical Patents Inc. Cationic polymerization catalysts
US5523359A (en) * 1995-01-13 1996-06-04 Exxon Chemical Patents Inc. Functionalized polymer and methods to obtain functionalized polymer
US5708103A (en) * 1995-02-01 1998-01-13 Kuraray Co., Ltd. Process for producing a polymer of vinylic compounds
US5721331A (en) * 1995-03-08 1998-02-24 Kuraray Co., Ltd. Isobutylene-based polymer and process of producing the same
US5741331A (en) * 1996-07-29 1998-04-21 Corvita Corporation Biostable elastomeric polymers having quaternary carbons
US6102939A (en) * 1996-07-29 2000-08-15 Corvita Corporation Method of implanting biostable elastomeric polymers having quaternary carbons
US6197240B1 (en) 1996-07-29 2001-03-06 Corvita Corporation Method of device having biostable elastomeric polymers having quaternary carbons
US5854367A (en) * 1996-09-26 1998-12-29 Arizona Chemical Company Process for cationic polymerization
WO1998013391A1 (en) * 1996-09-26 1998-04-02 Arizona Chemical Company Process for cationic polymerization
US6130291A (en) * 1998-06-04 2000-10-10 The University Of Akron Dynamic star polymers and a method for the synthesis thereof
US6274689B1 (en) 1998-10-07 2001-08-14 Exxon Chemical Patents, Inc. Random isomonoolefin/allyl styrene copolymers and functionalized derivatives thereof
US6265486B1 (en) 1998-12-31 2001-07-24 Exxon Mobil Chemical Patents Inc. Triblock copolymers incorporating a styrene/isoolefin copolymer midblock
US20100092540A1 (en) * 2000-12-12 2010-04-15 Boston Scientific Scimed, Inc. Drug delivery compositions and medical devices containing block copolymer
US20050215722A1 (en) * 2000-12-12 2005-09-29 Leonard Pinchunk Drug delivery compositions and medical devices containing block copolymer
US6545097B2 (en) 2000-12-12 2003-04-08 Scimed Life Systems, Inc. Drug delivery compositions and medical devices containing block copolymer
US20030171496A1 (en) * 2000-12-12 2003-09-11 Leonard Pinchuk Drug delivery compositions and medical devices containing block copolymer
US7923509B2 (en) 2000-12-12 2011-04-12 Boston Scientific Scimed, Inc. Drug delivery compositions and medical devices containing block copolymer
US6855770B2 (en) 2000-12-12 2005-02-15 Scimed Life Systems, Inc. Drug delivery compositions and medical devices containing block copolymer
US7622530B2 (en) 2000-12-12 2009-11-24 Boston Scientific Scimed, Inc. Drug delivery compositions and medical devices containing block copolymer
US20040063879A1 (en) * 2001-01-24 2004-04-01 Baird Michael C. Process for making high molecular weight isobutylene polymers
US20080275201A1 (en) * 2001-01-24 2008-11-06 Baird Michael C Process for making high molecular weight Isobutylene polymers
US7238819B2 (en) 2002-01-21 2007-07-03 Lanxess Inc. Process for preparing isobutylene-based polymers
US20050165182A1 (en) * 2002-01-21 2005-07-28 Manfred Bochmann Process for preparing isobutylene-based polymers
US7452939B2 (en) 2002-03-29 2008-11-18 San-Ei Kougyou Corporation Polyesterified block copolymer and process for producing the same
EP1491573A4 (en) * 2002-03-29 2005-09-21 Takashi Sawaguchi Novel polyesterified block copolymer and process for producing the same
US6844412B2 (en) 2002-07-25 2005-01-18 Lord Corporation Ambient cured coatings and coated rubber products therefrom
US20040018312A1 (en) * 2002-07-25 2004-01-29 Lord Corporation Ambient cured coatings and coated rubber products therefrom
US20060127198A1 (en) * 2002-09-11 2006-06-15 Bsh Bosch Und Siemens Hausgerate Gmbh Liquor container for a washing machine
US20040068036A1 (en) * 2002-10-07 2004-04-08 Halladay James R. Flexible emissive coatings for elastomer substrates
US6777026B2 (en) 2002-10-07 2004-08-17 Lord Corporation Flexible emissive coatings for elastomer substrates
US6969744B2 (en) 2003-06-19 2005-11-29 University Of Southern Mississippi Living and quasiliving cationic telechelic polymers quenched by N-substituted pyrrole and methods for their preparation
US20050282972A1 (en) * 2003-06-19 2005-12-22 Stokes Casey D Process for preparing terminally functionalized living and quasiliving cationic telechelic polymers
US7576161B2 (en) 2003-06-19 2009-08-18 Chevron Oronite Company Llc Process for preparing terminally functionalized living and quasiliving cationic telechelic polymers
US20040260033A1 (en) * 2003-06-19 2004-12-23 Stokes Casey D. Living and quasiliving cationic telechelic polymers quenched by N-substituted pyrrole and methods for their preparation
US20050143526A1 (en) * 2003-06-20 2005-06-30 Rudolf Faust End-capped polymer chains and products thereof
US7417092B2 (en) 2003-06-20 2008-08-26 University Of Massachusetts Lowell End-capped polymer chains and products thereof
US20070093604A1 (en) * 2003-07-01 2007-04-26 Joseph Kennedy Thermoplastic elastomeric multiblock copolymers of isobutylene and norbornene
US20050187414A1 (en) * 2003-07-31 2005-08-25 Rudolf Faust Copolymers comprising branched olefin and vinyl ether units
US20050125059A1 (en) * 2003-12-05 2005-06-09 Leonard Pinchuk Ocular lens
US7794498B2 (en) * 2003-12-05 2010-09-14 Innolene Llc Ocular lens
US20090312836A1 (en) * 2003-12-05 2009-12-17 Leonard Pinchuk Ocular Lens
US20050125003A1 (en) * 2003-12-05 2005-06-09 Leonard Pinchuk Glaucoma implant device
US7056985B2 (en) 2004-02-11 2006-06-06 University Of Massachusetts Lowell End-capped polymer chains and products thereof
US7226979B2 (en) 2004-02-11 2007-06-05 University Of Massachusetts Lowell Copolymers comprising olefin and protected or unprotected hydroxystyrene units
US7671158B2 (en) 2004-02-11 2010-03-02 University Of Massachusetts Lowell End-capped polymer chains and products thereof
US20060223946A1 (en) * 2004-02-11 2006-10-05 University Of Massachusetts Lowell End-capped polymer chains and products thereof
US20050176903A1 (en) * 2004-02-11 2005-08-11 Rudolf Faust End-capped polymer chains and products thereof
US20100168339A1 (en) * 2004-02-11 2010-07-01 Rudolf Faust Novel methods for forming copolymers comprising olefin and protected or unprotected hydroxystyrene units
US20050176891A1 (en) * 2004-02-11 2005-08-11 Rudolf Faust Copolymers comprising olefin and protected or unprotected hydroxystyrene units
US7709580B2 (en) 2004-08-20 2010-05-04 Chevron Oronite Company Llc Method for preparation of polylefins containing exo-olefin chain ends
US20060041081A1 (en) * 2004-08-20 2006-02-23 Chevron Oronite Company Llc Method for preparing polyolefins containing a high percentage of exo-olefin chain ends
US8530586B2 (en) 2004-08-20 2013-09-10 Chevron Oronite Company Llc Method for preparing polyolefins containing a high percentage of exo-olefin chain ends
US20060041084A1 (en) * 2004-08-20 2006-02-23 Chevron Oronite Company Llc Method for preparation of polyolefins containing exo-olefin chain ends
US7420019B2 (en) 2004-08-20 2008-09-02 Chevron Oronite Company Llc Method for preparation of polyolefins containing exo-olefin chain ends
EP2284202A2 (en) 2004-08-20 2011-02-16 Chevron Oronite Company LLC Method for preparing polyolefins containing a high percentage of exo-olefin chain ends
US7705090B2 (en) 2004-08-20 2010-04-27 Chevron Oronite Company Llc Method for preparing polyolefins containing a high percentage of exo-olefin chain ends
EP2284203A2 (en) 2004-08-20 2011-02-16 Chevron Oronite Company LLC Method for preparation of polyolefins containing exo-olefin chain ends
US20100311913A1 (en) * 2004-08-20 2010-12-09 Chevron Oronite Company Llc Method for preparing polyolefins containing a high percentage of exo-olefin chain ends
US20060041083A1 (en) * 2004-08-20 2006-02-23 Chevron Oronite Company Llc Method for preparation of polyolefins containing exo-olefin chain ends
US20060045900A1 (en) * 2004-08-27 2006-03-02 Robert Richard Embolization
US7837644B2 (en) 2004-12-03 2010-11-23 Innfocus, Llc Glaucoma implant device
US7594899B2 (en) 2004-12-03 2009-09-29 Innfocus, Llc Glaucoma implant device
US20070141116A1 (en) * 2004-12-03 2007-06-21 Leonard Pinchuk Glaucoma Implant Device
US20070123812A1 (en) * 2004-12-03 2007-05-31 Leonard Pinchuk Glaucoma Implant Device
US20070118066A1 (en) * 2004-12-03 2007-05-24 Leonard Pinchuk Glaucoma Implant Device
US7553546B1 (en) 2005-11-16 2009-06-30 Pacesetter, Inc. Polyethylene oxide and silicone copolymers and their usage on medical devices
US7715922B1 (en) 2005-11-16 2010-05-11 Pacesetter, Inc. Polyethylene oxide and polyisobutylene copolymers and their usage on medical devices
US7708774B1 (en) 2005-11-16 2010-05-04 Pacesetter, Inc. Polyethylene oxide and silicone copolymers and their usage on medical devices
US20070141340A1 (en) * 2005-12-21 2007-06-21 Young-Ho Song Block copolymer particles
US7501179B2 (en) 2005-12-21 2009-03-10 Boston Scientific Scimed, Inc. Block copolymer particles
US7947368B2 (en) 2005-12-21 2011-05-24 Boston Scientific Scimed, Inc. Block copolymer particles
US20070141339A1 (en) * 2005-12-21 2007-06-21 Young-Ho Song Block copolymer particles
US20070142560A1 (en) * 2005-12-21 2007-06-21 Young-Ho Song Block copolymer particles
US8013073B2 (en) 2005-12-30 2011-09-06 Chevron Oronite Company Llc Method for preparing polyolefins containing vinylidine end groups using nonaromatic heterocyclic compounds
US20070155908A1 (en) * 2005-12-30 2007-07-05 Stokes Casey D Method for preparing polyolefins containing vinylidine end groups using azole compounds
US20070155911A1 (en) * 2005-12-30 2007-07-05 Stokes Casey D Method for preparing polyolefins containing vinylidine end groups using nonaromatic heterocyclic compounds
US20070155910A1 (en) * 2005-12-30 2007-07-05 Chevron Oronite Company Llc Method for preparing polyolefins containing vinylidine end groups using polymeric nitrogen compounds
US7816459B2 (en) 2005-12-30 2010-10-19 Chevron Oronite Company Llc Method for preparing polyolefins containing vinylidine end groups using polymeric nitrogen compounds
US7501476B2 (en) 2005-12-30 2009-03-10 Chevron Oronite Company, Llc Method for preparing polyolefins containing vinylidene end groups using azole compounds
EP1932859A2 (en) 2006-12-15 2008-06-18 Chevron Oronite Company LLC Polyisobutenyl sulfonates having low polydispersity
US20090068271A1 (en) * 2007-09-12 2009-03-12 Boston Scientific Scimed, Inc. Embolization particles
EP2712809A1 (en) 2007-10-19 2014-04-02 Lord Corporation Suspension system for aircraft auxilliary power unit with elastomeric member
EP2712808A1 (en) 2007-10-19 2014-04-02 Lord Corporation Suspension system for aircraft auxiliary power unit with elastomeric member
US8394897B2 (en) 2008-03-25 2013-03-12 Chevron Oronite Company Llc Production of vinylidene-terminated polyolefins via quenching with monosulfides
US20090247716A1 (en) * 2008-03-25 2009-10-01 Stokes Casey D Production of Vinylidene-Terminated Polyolefins Via Quenching with Monosulfides
US8063154B2 (en) 2008-06-24 2011-11-22 The University Of Southern Mississippi Preparation of exo-olefin terminated polyolefins via quenching with alkoxysilanes or ethers
US20090318624A1 (en) * 2008-06-24 2009-12-24 Storey Robson F Preparation of exo-olefin terminated polyolefins via quenching with alkoxysilanes or ethers
US8501831B2 (en) 2008-06-27 2013-08-06 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical devices containing the same
US20110166425A1 (en) * 2008-09-05 2011-07-07 Edelman David S Flexible Disposable Surgical Port
US8895672B2 (en) 2008-10-22 2014-11-25 Chevron Oronite Company Llc Production of vinylidene-terminated and sulfide-terminated telechelic polyolefins via quenching with disulfides
US8383760B2 (en) 2008-10-22 2013-02-26 Chevron Oronite Company Llc Production of vinylidene-terminated and sulfide-terminated telechelic polyolefins via quenching with disulfides
US8133954B2 (en) 2008-10-22 2012-03-13 Chevron Oronite Company Llc Production of vinylidene-terminated and sulfide-terminated telechelic polyolefins via quenching with disulfides
US20100099835A1 (en) * 2008-10-22 2010-04-22 Stokes Casey D Production of Vinylidene-Terminated and Sulfide-Terminated Telechelic Polyolefins Via Quenching with Disulfides
US8507641B2 (en) 2008-10-22 2013-08-13 Chevron Oronite Company Llc Production of vinylidene-terminated and sulfide-terminated telechelic polyolefins via quenching with disulfides
US11174336B2 (en) 2009-01-12 2021-11-16 University Of Massachusetts Lowell Polyisobutylene-based polyurethanes
US8962785B2 (en) 2009-01-12 2015-02-24 University Of Massachusetts Lowell Polyisobutylene-based polyurethanes
US10513576B2 (en) 2009-01-12 2019-12-24 University of Masschusetts Lowell Polyisobutylene-based polyurethanes
US8344073B2 (en) 2009-01-16 2013-01-01 The University Of Southern Mississippi Functionalization of polyolefins with phenoxy derivatives
US9650449B2 (en) 2009-01-16 2017-05-16 The University Of Southern Mississippi Functionalization of polyolefins with phenoxy derivatives
US9315595B2 (en) 2009-03-31 2016-04-19 Chevron Oronite Company Llc Amine-terminated telechelic polymers and precursors thereto and methods for their preparation
WO2010117619A2 (en) 2009-03-31 2010-10-14 Chevron Oronite Company Llc Amine-terminated telechelic polymers and precursors thereto and methods for their preparation
US20100249001A1 (en) * 2009-03-31 2010-09-30 Storey Robson F Amine-terminated telechelic polymers and precursors thereto and methods for their preparation
US8552122B2 (en) 2009-03-31 2013-10-08 The University Of Southern Mississippi Amine-terminated telechelic polymers and precursors thereto and methods for their preparation
CN101955558B (en) * 2009-07-15 2013-03-13 北京化工大学 Initiating system for preparing high-reaction activity polyisobutene and copolymer of polyisobutene
US8394898B2 (en) 2009-07-31 2013-03-12 The University Of Southern Mississippi In situ formation of hydroxy chain end functional polyolefins
US9150672B2 (en) 2009-07-31 2015-10-06 The University Of Southern Mississippi In situ formation of hydroxy chain end functional polyolefins
US20110028681A1 (en) * 2009-07-31 2011-02-03 Storey Robson F In situ formation of hydroxy chain end functional polyolefins
US8927660B2 (en) 2009-08-21 2015-01-06 Cardiac Pacemakers Inc. Crosslinkable polyisobutylene-based polymers and medical devices containing the same
US20130131767A1 (en) * 2009-09-02 2013-05-23 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same
US20140194963A1 (en) * 2009-09-02 2014-07-10 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same
US20110054580A1 (en) * 2009-09-02 2011-03-03 Shrojalkumar Desai Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same
US8942823B2 (en) 2009-09-02 2015-01-27 Cardiac Pacemakers, Inc. Medical devices including polyisobutylene based polymers and derivatives thereof
US8903507B2 (en) * 2009-09-02 2014-12-02 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same
US8676344B2 (en) * 2009-09-02 2014-03-18 Cardiac Pacemakers Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same
US8374704B2 (en) * 2009-09-02 2013-02-12 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same
US20110060082A1 (en) * 2009-09-08 2011-03-10 Mutsuki Sugimoto Polymer composition and pneumatic tire
US8158705B2 (en) 2009-09-08 2012-04-17 Sumitomo Rubber Industries, Ltd. Polymer composition and pneumatic tire
US20110056612A1 (en) * 2009-09-10 2011-03-10 Mutsuki Sugimoto Method for Producing Polymer Sheet for Inner Liner and Method for Producing Pneumatic Tire
US8597561B2 (en) 2009-09-18 2013-12-03 Sumitomo Rubber Industries, Ltd. Method for producing pneumatic tire
US20110068508A1 (en) * 2009-09-18 2011-03-24 Mutsuki Sugimoto Method for producing pneumatic tire
US8835557B2 (en) 2009-09-30 2014-09-16 Sumitomo Rubber Industries, Ltd. Polymer composition for inner liner and pneumatic tire using the same
US20110077357A1 (en) * 2009-09-30 2011-03-31 Mutsuki Sugimoto Polymer composition for inner liner and pneumatic tire using the same
WO2011075536A2 (en) 2009-12-18 2011-06-23 Chevron Oronite Company Llc Carbonyl-ene functionalized polyolefins
US8492491B2 (en) 2010-06-10 2013-07-23 Chevron Oronite Company Llc Methods for producing telechelic polyolefins from terpene initiators
US9187581B2 (en) 2010-06-10 2015-11-17 Chevron Oronite Company Llc Methods for producing telechelic polyolefins from terpene initiators
US8937134B2 (en) 2010-06-14 2015-01-20 The University Of Southern Mississippi Vinyl ether end-functionalized polyolefins
US8592527B2 (en) 2010-06-14 2013-11-26 University Of Southern Mississippi Vinyl ether end-functionalized polyolefins
US8815033B2 (en) 2010-06-29 2014-08-26 Sumitomo Rubber Industries, Ltd. Method for producing pneumatic tire and pneumatic tire
US8893756B2 (en) 2010-07-07 2014-11-25 Sumitomo Rubber Industries, Ltd. Polymer sheet for inner liner and pneumatic tire using the same
US8656973B2 (en) 2010-07-30 2014-02-25 Sumitomo Rubber Industries, Ltd. Polymer sheet for inner liner, polymer laminate for inner liner, and pneumatic tire
US10239271B2 (en) 2010-11-05 2019-03-26 Sumitomo Rubber Industries, Ltd. Strip, method for manufacturing the same, and method for manufacturing pneumatic tire
US10046532B2 (en) 2010-11-17 2018-08-14 Sumitomo Rubber Industries, Ltd. Method for manufacturing pneumatic tire
US9676234B2 (en) 2010-12-06 2017-06-13 Sumitomo Rubber Industries, Ltd. Strip, method for manufacturing the same, and method for manufacturing pneumatic tire
US8660663B2 (en) 2010-12-20 2014-02-25 Cardiac Pacemakers, Inc. Lead having a conductive polymer conductor
US8969484B2 (en) 2011-07-08 2015-03-03 Chevron Oronite Company Llc Methods of producing mono- and multi-functional polymers from terpene-based initiators
US9855798B2 (en) 2011-07-28 2018-01-02 Sumitomo Rubber Industries, Ltd. Pneumatic tire
US10596036B2 (en) 2012-01-12 2020-03-24 Innfocus, Inc. Device for treating glaucoma
WO2013147978A2 (en) 2012-01-12 2013-10-03 Innfocus, Inc. Method, surgical kit and device for treating glaucoma
US9889042B2 (en) 2012-01-12 2018-02-13 Innfocus, Inc. Method, surgical kit and device for treating glaucoma
US11717441B2 (en) 2012-01-12 2023-08-08 Innfocus, Inc. Device for treating glaucoma
EP3329884A1 (en) 2012-01-12 2018-06-06 Innfocus, Inc. Implantable device for treating glaucoma
US10772762B2 (en) 2012-01-12 2020-09-15 Innfocus, Inc. Device for treating glaucoma
EP3919030A1 (en) 2012-01-12 2021-12-08 Innfocus, Inc. Implantable device for treating glaucoma
US9101444B2 (en) 2012-01-12 2015-08-11 Innfocus, Inc. Method, surgical kit and device for treating glaucoma
US10729583B2 (en) 2012-01-12 2020-08-04 Innfocus, Inc. Device for treating glaucoma
US10272721B2 (en) 2012-08-01 2019-04-30 Sumitomo Rubber Industries, Ltd. Pneumatic tire including inner liner
US9023970B2 (en) * 2012-10-12 2015-05-05 Basf Se Process for preparing polyisobutenes
US20140107310A1 (en) * 2012-10-12 2014-04-17 Basf Se Process for preparing polyisobutenes
US10562998B2 (en) 2012-11-21 2020-02-18 University Of Massachusetts High strength polyisobutylene polyurethanes
US9926399B2 (en) 2012-11-21 2018-03-27 University Of Massachusetts High strength polyisobutylene polyurethanes
US10526429B2 (en) 2017-03-07 2020-01-07 Cardiac Pacemakers, Inc. Hydroboration/oxidation of allyl-terminated polyisobutylene
US10835638B2 (en) 2017-08-17 2020-11-17 Cardiac Pacemakers, Inc. Photocrosslinked polymers for enhanced durability
US11472911B2 (en) 2018-01-17 2022-10-18 Cardiac Pacemakers, Inc. End-capped polyisobutylene polyurethane
US11851522B2 (en) 2018-01-17 2023-12-26 Cardiac Pacemakers, Inc. End-capped polyisobutylene polyurethane

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